Indian Journal
of Chemistry
Sect. A: Inorganic, Bioinorganic, Physical, Theoretical & Analyticalhttp://www.niscair.res.in; http://nopr.niscair.res.in Total visitors: 2625 since 882014
CODEN: ICACEC; ISSN: 03764710 (Print), 09750975
(Online)
Special Issue on Chemical Reactivity Theory 
VOLUME 53A 
NUMBER 89 
AUGSEPT 2014 

CONTENTS 

929 
Is it impossible to find the universal density
functional? Or is it just wellhidden? Paul W Ayers* & Robert G Parr^{} 

While it is generally accepted that no explicit analytic form for the
exact functional exists, it is argued, based on what is known about the
classical manybody problem, that this is not necessarily the case. 

932 
Thoughts
upon the approaching thirtieth anniversary of two seminal coordinate scaling
papers in density functional theory 

The significance of two seminal papers
on coordinate scaling in density functional theory, [Levy & Perdew, Phys Rev A, 32 (1985) 2010 and Ghosh & Parr, J Chem Phys, 82 (1985) 3307], is discussed. 

933 
Limits of the concept of reactivity 

Despite the usefulness of
concepts related to reactivity, finding a universal solution is hampered by the very nature of the problem;
reactants behave differently under the influence of different reactants. Key elements in producing
this diversity are degeneracy and the irrelevance of asymptotic
behavior for understanding equilibrium points on the potential energy
surface. 

936 
Hypervirial theorems and scaling relations in density
functional theory 

Within the framework of density functional
theory, a hypervirial theorem for an operator Â is derived. The result
involves the single particle electron density, r(r), and the
chemical potential operator, m, of a manyelectron system. Generalized scaling
relations for the energy density functionals are also discussed. 

940 
High reactivity of triazolinediones
as superelectrophiles in polar reactions: A DFT study Luis R Domingo* & Saeed
R Emamian




949 
Evaluation of hardness in KohnSham theory with local
density and generalized gradient approximations José L Gázquez*, Badhin Gómez, 

Hardness of chemical species is calculated without using the frontier
eigenvalues of LDA or GGA calculations. 

958 
Average local ionization potential within the
framework of the electron localization function 

A model intended to be a measure of the average local
vertical ionization energy associated with the electron localization function
valence population basins is explored. Comparison of computational results
with the available experimental data for simple substituted isothiocyanates,
provides new insights within the field for validating relationships between
the spatial topology of electronic populations and energetic aspects of the
bonding. 

965 
Local thermodynamical formalism for ensembles of
excited states 

The
thermodynamical formalism of density functional theory is generalized for
ensembles of excited states. A family of novel descriptors of Coulomb systems
is introduced. 

970 
On the relationship among
GhoshBerkowitzParr entropy, Chunying Rong, Tian Lu, Pratim K Chattaraj* &
Shubin Liu*


The intrinsic
relationship of the GhoshBerkowitzParr entropy with 

978 
Structural similarity between boron oxide B_{n}(BO)_{n}^{2–}
and boron hydride B_{n}H_{n}^{2–} dianions (n = 4–12) Truong Ba Tai, Nguyen Minh Tam & 

There are
intriguing structural similarities between boron oxides B_{n}(BO)_{n}^{2–}
and boron hydride B_{n}H_{n}^{2–} dianions. The global minima of the small species, B_{n}(BO)_{n}^{2–}
(n = 4–6) are analogous to those of
boron hydride dianions, B_{n}H_{n}^{2–}. The enhanced
stabilities for the dianionic clusters, B_{n}(BO)_{n}^{2–}
at n = 6, 10 and 12, follow a trend
similar to that of the boron hydride dianions, B_{n}H_{n}^{2–}. 

985 
Quantifying dispersion interaction: A study of alkane
and alkene dimers J Richard Premkumar, Deivasigamani Umadevi & 

Both acyclic and cyclic hydrocarbon dimers are mainly
stabilized by dispersion interaction. The dispersion energy is higher for
alkane dimers for acyclic systems, while in cyclic systems a reversal of this
trend is observed. 

992 
On the nature of CH_{6}^{2+} 



996 
Enhanced interaction of molecular oxygen
with amino acid complexes of silver and gold clusters 

Adsorption of amino acids, glycine and alanine,
enhances the reactivity of Ag_{4} and Au_{4} clusters towards
O_{2} molecule, which is manifested by an increase in the O_{2}
binding energy and a decrease in the M–O (M = Ag, Au) bond length. The extent
of interaction is more in the case of the Au_{4} cluster. Also,
the coadsorption of amino acids and O_{2} molecule on the Ag_{4}
and Au_{4} clusters is cooperative. 

1001 
Unraveling the reaction mechanism, enantio
and diastereoselectivities of selenium ylide promoted epoxidation Madhavan Jaccob, Gopal
Sabapathi,^{
}J Vijaya Sundar, P Kolandaivel*, V Subramanian* 

DFT calculations shows that
initial addition transition state is the key step for deciding the
enantioselectivity of the chiral selenium ylide mediated epoxidation, which
is mainly governed by the steric interactions. 

1010 
Quantum information description of reactive systems 

Directions of the equilibrium
current of the 

1019 
Electrostatics and tailoring for
aggregation of small linear molecules: An ab
initio study Gurmeet Singh & Shridhar R Gadre*


MESP features of CO_{2}, CS_{2} and OCS are utilized for a comparative study of their aggregations into small clusters. 

1031 
Electronic stress tensor of chemical bond 

The theory of electronic stress tensor of chemical bond on the variation principle of gravity
using the semiclassical action integral has been extended to the
theory using a quantum action integral based on a simple SUGRA model of gravity. The
central symmetrical properties of the theory are found to be intact. 

1036 
A gradientbased trust radius update suitable for
saddle point and transition state optimization 

A new trust radius
method, appropriate for saddle point optimization is proposed. The method
ensures that the gradients from the quadratic model and the exact computed
gradients are similar in direction and magnitude. For transition state
optimization, the new trust radius method is found to be somewhat better than
more traditional methods, based on the value of the objective function.
Cosine between two vectors 

1043 
Soft nuclear density and nuclear repulsion 

Substitution of the pointlike charges by
soft nuclear charges in the nuclear contribution to the total molecular
energy under the BornOppenheimer approximation is discussed. The soft
nuclear charge distribution is represented by Minkowski normalized Gaussian
functions, centered at each nucleus. The general formalism is well suited to
be included in ab initio
calculations in a Gaussian basis LCAO MO framework, indicating that the
molecular total energy surfaces must have preserved the general features, but
with the new features in the absence of singularities. 

1052 
Polarization, reactivity and quantum molecular capacitance: From
electrostatics to density functional theory Patrice Delarue & Patrick Senet*


The electron density induced by a
potential has delocalized contribution proportional to the 

1058 
Solvation of
graphene sheets vs. dimerization: 



1064 




Authors for correspondence are indicated by (*)
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 929931
Is it impossible to find the universal density functional? Or is it just
wellhidden?
Paul W Ayers^{a, }* & Robert G Parr^{b}
^{a}Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario, Canada L8S 4M1
Email:ayers@mcmaster.ca
^{b}Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, USA
Email:rgparr@email.unc.edu
Received 21 April 2014; revised and accepted 11 May 2014
We review information on methods for constructing the exact density functional mathematically and computationally. While it is generally accepted that no explicit analytic form for the exact functional exists, we argue, based on what is known about the classical manybody problem, that this is not necessarily the case.
Keywords: Theoretical
chemistry, Density functional calculations, Universal density functional,
Electron density
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 932
Thoughts upon the approaching thirtieth anniversary of
two seminal
coordinate scaling papers in density functional
theory
Mel Levy
Department of Chemistry, Duke University, Durham, North
Carolina 27708, USA
Department of Physics, North Carolina A and T State
University, Greensboro, North Carolina 27411, USA
Department of Chemistry and Quantum Theory Group, Tulane
University, New Orleans, Louisiana 70118
Email: mlevy@tulane.edu; mplevy@ncat.edu
Received 3 July 2014; accepted 4 July 2014
The significance of
two seminal papers on coordinate scaling in density functional theory, [Levy M &
Perdew J P, Phys Rev A, 32 (1985)
2010 and Ghosh S K & Parr R G, J Chem
Phys, 82 (1985) 3307] is discussed.
Keywords: Theoretical chemistry, Density functional
calculations, Coordinate scaling, Scaling
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 933935
Limits of the concept of reactivity
Andreas Savin
CNRS, UMR7616,
Laboratoire de Chimie Théorique, F75005 Paris, France
Sorbonne Universités, UPMC Univ Paris 06, UMR7616, Laboratoire de Chimie Théorique, F75005 Paris, France
Email: andreas.savin@lct.jussieu.fr
Received 17 April 2014; accepted 22 April 2014
In spite of the usefulness of concepts related to reactivity, finding of a universally applicable recipe is hampered by the very nature of the problem, reactants behave differently under the influence of different reactants. Key elements in producing this diversity are degeneracy, and the irrelevance of asymptotic behavior for understanding equilibrium points on the potential energy surface. Simple examples are given to illustrate it.
Keywords: Theoretical chemistry, Chemical reactivity,
Degeneracy, Quantum entanglement
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 936939
Hypervirial theorems and scaling relations in density functional theory
Swapan K Ghosh
Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400 085, India
Email: skghosh@barc.gov.in
Received 29 May 2014:
accepted 29 May 2014
Within the framework of density functional theory, a hypervirial theorem for an operator is shown to be given by ∫dr r(r)^{1/2} [m,] r(r)^{1/2 }= 0, where r(r) is the single particle electron density of a manyelectron system. The chemical potential operator m expressed as either a multiplicative or a differential operator, depending on the variant of DFT, is shown to yield equivalent results. The consequence of using approximate forms of the energy density functionals are discussed and for special cases of the operator , the virial theorem in DFT is recovered. Generalised scaling relations for the energy density functionals are obtained and the implications towards tensor virial theorem are discussed.
Keywords: Theoretical chemistry, Density functional
calculations, Hypervirial theorem
Indian Journal of
Chemistry
Vol. 53A, AugSept 2014, pp.
940948
High reactivity of triazolinediones as
superelectrophiles in
polar reactions: A DFT study
Luis R
Domingo^{a, }* & Saeed R Emamian^{b}
^{a}Departamento de Química Orgánica, Universidad de Valencia, Dr Moliner
50, E46100 Burjassot,
Email: domingo@utopia.uv.es
^{b}Chemistry
Department, Shahrood Branch, Islamic Azad University,
Received 28 March 2014; revised and accepted 14 April 2014
The mechanism of the polar
reaction between the superelectrophile PTAD (2) and diene (6b) in the presence of THF has
theoretically been studied at the MPWB1K/6311G**
level. Our investigations reveal that this reaction takes place through a
stepwise mechanism via
formation of intermediate (7b) with
a strong zwitterionic character. The first step of the reaction, which is
associated with the nucleophilic attack of diene (6b) on PTAD (2), presents complete endo
selectivity. Formation of the expected formal
Keywords: Theoretical chemistry, Chemical reactivity,
Superelectrophiles, Density functional calculations, Triazolinediones
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 949957
Evaluation of hardness in KohnSham theory
with local density and
generalized gradient approximations
José L Gázquez^{a, }*, Badhin Gómez^{a}, Fernando D Hinojosa^{b} & Alberto Vela^{b}
^{a}Departamento
de Química, Universidad Autónoma MetropolitanaIztapalapa,
Av. San Rafael Atlixco 186,
México, D. F. 09340, México
Email: jlgm@xanum.uam.mx
^{b}Departamento de
Química, Centro de Investigación y de Estudios Avanzados,
Av. Instituto Politécnico Nacional 2508, México, D. F.
07360, México
Received 29 April 2014; revised and accepted 3 June 2014
By making use
of Janak’s interpolation in the KohnSham method, together with an explicit and
differentiable functional of the density for the exchangecorrelation energy,
like LDA or GGA, the second derivative of the energy with respect to the number
of electrons, N, is evaluated from the derivative of the highest
occupied molecular orbital (HOMO) with respect to N (left derivative),
or from the derivative of the lowest unoccupied molecular orbital (LUMO) with
respect to N (right derivative). Both cases lead to expressions that may
be evaluated from a single postSCF calculation that avoids the use of the
frontier orbitals eigenvalues. The results obtained for two test sets of
molecules and for several atoms indicate that both provide a better description
than the LUMOHOMO eigenvalue difference and that the left derivative seems to
lead to more confident results than the right derivative.
Keywords: Theoretical chemistry, Density functional
calculations, KohnSham theory, Chemical reactivity, Chemical potential,
Hardness, Softness
Indian Journal of
Chemistry
Vol. 53A, AugSept 2014, pp. 958964
Average local ionization potential within the
framework of the
electron localization function
Eduardo Chamorro^{a, }*, Patricia
Pérez^{a}, Mario DuqueNoreña^{a}, Pierre Paul Romagnoli^{b},
Daniel Pons^{b} & Mauricio González^{c }
^{a}Departamento de Ciencias Quimicas, ^{b}Departmento de Matematicas, ^{c }Departamento de Física, Facultad de Ciencias Exactas, Universidad Andres Bello. Avenida República 275, 8370146, Santiago, Chile
Email: echamorro@unab.cl
Received 25April 2014; revised and accepted 9 May 2014
In this work we explore new insights arising from simple indices intended to measure the average local vertical ionization energy associated to ELF valence population basins. The model has been computationally tested on simple isothiocyanate compounds (RN=C=S) revealing that the proposed relationships correctly establish both the inductive and electronegativity effects of electronegative groups along the examined series, i.e., methyl < germyl < hydrogen < acetyl < chlorodifluoroacetyl, in agreement with the available experimental observations. The proposed energetical descriptors are expected to contribute to the search of relationships between the spatial topology of electronic populations and energetical aspects of the bonding. The present results enhance the possibility of gaining insight into chemical bonding and reactivity within the ELF topologicaldefined framework of chemical rationalization.
Keywords: Theoretical chemistry, Ionization potential, Electron
localization function, Chemical reactivity, Nucleophilicity, Isothiocyanates,
Valence basin populations, Lone pairs
Indian Journal of
Chemistry
Vol. 53A, AugSept 2014, pp. 965969
Local thermodynamical formalism for ensembles of excited states
Á Nagy
Department of Theoretical Physics, University of Debrecen, Debrecen, Hungary
Email: anagy@phys.unideb.hu
Received 28 March 2014; revised and accepted 7 April 2014
The thermodynamical formalism of density functional theory is generalized for ensembles of excited states. Ensemble local temperature is defined. A family of novel descriptors of Coulomb systems is introduced.
Keywords: Theoretical chemistry, Density functional
calculations, Excited states
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 970977
On the relationship among GhoshBerkowitzParr
entropy,
Shannon entropy and Fisher information
Chunying Rong^{a}, Tian Lu^{b}, Pratim K Chattaraj^{c, }* & Shubin Liu^{a, d, }*^{}
^{a}Key Laboratory of Chemical Biology and Traditional Chinese Medicine
Research (Ministry of Education of China)
and Key Laboratory of Resource FineProcessing and Advanced Materials of Hunan
Province, College of Chemistry
and Chemical Engineering, Hunan Normal University, Changsha Hunan 410081, PR
China
^{b}School of Chemical and Biological Engineering, University of Science and Technology Beijing, Beijing, PR China
^{c}Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology, Kharagpur 721 302, India
Email: pkc@chem.iitkgp.ernet.in
^{d}Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 275993420, USA
Email: shubin@email.unc.edu
Received 11 April 2014; revised and accepted 15 May 2014
In their seminal work thirty years ago, Ghosh, Berkowitz, and Parr reformulated the groundstate densityfunctional theory into a local version of thermodynamics, where a new concept, called GhoshBerkowitzParr entropy, was proposed. Employing the noninteracting kinetic energy density and ThomasFermi kinetic energy density, this entropy was formulated like the SackurTetrode equation in classical thermodynamics. Not much has been known about its properties. In this contribution, we investigate its relationship with Shannon entropy and Fisher information from the numerical perspective. To that end, we have examined 36 neutral atoms and 42 molecular systems. We have considered both molecular and atomic contributions with Bader’s zeroflux criterion to partition atoms in molecules. Our results show that these quantities are closely correlated, and yet their correlations might be complicated since no universal relationship among them has been observed.
Keywords: Theoretical chemistry, Density functional
calculations, Entropy, GhoshBerkowitzPan entropy, Shannon entropy, Fisher
information, Electron density
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 978984
^{ }
^{ }
Structural
similarity between boron oxide B_{n}(BO)_{n}^{2–} and
boron hydride B_{n}H_{n}^{2–} dianions (n = 4–12)
Truong Ba Tai^{ a},^{ }Nguyen Minh Tam^{ a, b} & Minh Tho Nguyen^{a, b, }*^{}
^{a}Department of Chemistry, KU Leuven, B3001 Leuven, Belgium^{}
^{b}Institute for Computational Science and Technology at Ho Chi Minh City (ICST), Vietnam^{}
Email: minh.nguyen@chem.kuleuven.be
Received 8 April 2014; revised and accepted 13 April 2014
The boron oxide dianions B_{n}(BO)_{n}^{2–} (n = 4–12) are studied using DFT (B3LYP) method. Geometries of the global minima of B_{n}(BO)_{n}^{2–} with n = 4–12 are found to be analogous to those of boron hydrides. All boron oxides considered exhibit large HOMOLUMO gaps and high vertical detachment energies. Similar to B_{n}H_{n}^{2–}, the enhanced thermodynamic stabilities are established for B_{n}(BO)_{n}^{2–} at n = 6, 10 and 12. Due to the strength of BO bonds, oxidation of boron clusters thus consistently leads to formation of exohedral boronyls that in turns behave as substituents replacing the hydrogen atoms. This structural similarity allows the shape of boron oxides to be predicted from boron hydrides. Nevertheless, the BO bonds are expected to be the preferred reaction sites of boron oxides.
Keywords: Theoretical chemistry, Boron oxides, Boron
hydrides, Exohedral boronyls, Structural similarity
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 985991
Quantifying dispersion interaction: A study of alkane and alkene dimers
J Richard Premkumar, Deivasigamani Umadevi & G Narahari Sastry*
CSIRCentre for Molecular Modelling, Indian Institute
of Chemical Technology, Hyderabad 500 607, India
Email: gnsastry@gmail.com
Received 20 April 2014; revised and accepted 2 May 2014
In this study,
the interaction pattern and energies of a series of hydrocarbon dimers have
been investigated by using a highly reliable quantum chemical method
(M062X/ccpVTZ). Saturated and unsaturated hydrocarbons in both cyclic and
acyclic forms have been modelled to study their interaction. These dimers are
found to involve different types of noncovalent interactions such as pp (dimer of
unsaturated hydrocarbons), CH×××p (dimer of saturatedunsaturated
hydrocarbons) and CH×××HC (dimer of saturated hydrocarbons).
Atoms in molecules analysis provides further insight into the presence of these
different noncovalent interactions. Interestingly, the saturated hydrocarbon
dimers (AA) are found to have binding energy strengths comparable with those
of the dimers of their unsaturated counterparts (EE). Strong interactions have
been observed between the saturated monomers with the corresponding unsaturated
monomers (AE). The energy decomposition analysis using DFTSAPT method reveals
that both dispersion and electrostatic components play nearly equal roles in
modulation of the strength of the hydrocarbonhydrocarbon interaction.
Keywords: Theoretical chemistry, Density functional
calculations, Dispersion, Noncovalent interactions, Hydrocarbon interactions,
Alkane dimers, Alkene dimers, Dimers, Hydrocarbon dimers,
Energy decomposition analysis
^{ }
Indian
Journal of Chemistry
Vol. 53A,
AugSept 2014, pp. 992995
On the nature of CH_{6}^{2+}
Said Jalife^{a},
Rafael GrandeAztatzi^{a}, Diego Moreno^{a}, María A
FernándezHerrera^{b}, Edison Osorio^{c}, Sudip Pan^{d},
Paul von Ragué Schleyer^{ e}, Gerardo MartínezGuajardo^{a, f, }*
& Gabriel Merino^{a, }*
^{a}Departamento de Física Aplicada, Centro de
Investigación y de Estudios Avanzados,
Unidad Mérida. Km 6 Antigua Carretera a Progreso Apdo. Postal 73, Cordemex,
97310, Mérida, Yucatán, México
Email: gmerino@mda.cinvestav.mx
^{b}Facultad de Ciencias Químicas, Benemérita
Universidad Autónoma de Puebla. Ciudad Universitaria, 72570, Puebla, México
^{c}Departamento
de Ciencias Básicas, Fundación Universitaria Luis Amigó, SISCO, Transversal 51A
# 67B 90,
Medellín, Colombia
^{d}Department of Chemistry and Centre for Theoretical Studies, Indian
Institute of Technology Kharagpur,
Kharagpur 721 302, India
^{e}Center for Computational Chemistry,
^{f}Unidad Académica de
Ciencias Químicas, Área de Ciencias de la Salud, Universidad Autónoma de Zacatecas, Km. 6 carretera ZacatecasGuadalajara s/n, Ejido La Escondida C P 98160, Zacatecas, México
Email: germtz86@gmail.com
Received 26 April 2014, revised and accepted 18 May 2014
The
metastability of the hexacoordinate CH_{6}^{2+} dication in
the gas phase is confirmed by a detailed computational exploration of its
potential energy surface, using a modified “Kick” heuristic methodology and by
BornOppenheimer MolecularDynamics simulations to assess its kinetic persistence.
The transition states for
deprotonation, decomposition into CH_{3}^{+} and H_{3}^{+},
hydrogen scrambling, and HH rotation are found. In addition, a nearly perfect
correlation between the protonation affinities and their coordination number is
obtained.
Keywords: Theoretical
chemistry, Kick heuristic methodology, BornOppenheimer molecular dynamics
study,
Kinetic stability, Adaptive natural density partitioning analysis
Indian Journal of Chemistry
Vol.
53A, AugSept 2014, pp. 9961000
Enhanced
interaction of molecular oxygen with amino acid complexes
of silver and gold clusters
Dar Manzoor & Sourav Pal*
Theoretical Chemistry
Group, CSIRNational Chemical Laboratory, Pune 411 008, India
Email: s.pal.ncl.res.in
Received
19 April 2014 ; accepted 13 May 2014
Density functional
theory calculations have been carried out to study the effect of amino acid
adsorption on the reactivity of silver and gold clusters with molecular oxygen.
It is found that the amino acids glycine and alanine form stable complexes with
both Ag_{4} and Au_{4} clusters. However, the extent of
interaction is more in the case of the Au_{4} cluster, as reflected
from the increase in binding energy in the amino acid Au_{4} complexes.
Our results confirm that the adsorption of amino acids glycine and alanine
enhances the reactivity of Ag_{4} and Au_{4} clusters towards O_{2}
molecule. The enhanced reactivity of O_{2} molecule towards the amino
acid metal cluster complexes is manifested by an increase in the O_{2}
binding energy and a decrease in the M–O (M = Ag, Au) bond length. Moreover, it
is found that the coadsorption of amino acids and O_{2} molecule on
the Ag_{4} and Au_{4} clusters is cooperative.
Keywords: Theoretical chemistry, Density functional calculations, Metal
clusters, Gold clusters, Silver clusters,
Amino acid complexes
Indian Journal of Chemistry
Vol. 53A,
AugSept 2014, pp. 10011009
Unraveling the reaction mechanism, enantio
and diastereoselectivities of
selenium ylide promoted epoxidation
Madhavan Jaccob^{a,
†}, Gopal Sabapathi^{a}, J Vijaya Sundar^{b}, P Kolandaivel^{c,
}*, V Subramanian^{b, }* &
Ponnambalam Venuvanalingam^{a, }*
^{a}Theoretical
and Computational Chemistry Laboratory, School of Chemistry, Bharathidasan
University,
Tiruchirappalli 620 024, Tamil Nadu, India
Email:
venuvanalingam@yahoo.com
^{b}Chemical Laboratory, CSIRCentral Leather
Research Institute, Adyar, Chennai 600 020, Tamil Nadu, India
Email:
subuchem@hotmail.com
^{c}Department
of Physics, Bharathiar University, Coimbatore 641 046, Tamil Nadu, India
Email: ponkvel@hotmail.com
Received 22 April 2014;
revised and accepted 10 May 2014
The reaction between chiral selenium ylide and benzaldehyde leads to the formation of (2S,3S)transepoxide with high enantio and diastereoselectivity. Density functional theory and HartreeFock calculations using 631G(d) basis set have been performed to understand the reaction mechanism and factors associated with enantio and diastereoselectivities. Conformation of chiral selenium ylide has been found to have a strong influence on the stability of the initial addition transition state between ylide and benzaldehyde. Calculated enantio and diastereoselectivities from the energy differences between B3LYP/631G(d) addition TSs are in good agreement with the experimental data. The rate and diastereoselectivity are controlled by the cisoidtransoid rotational transition state. Analysis of transition state geometries clearly reveals that unfavorable eclipsing interaction between phenyl groups of the benzaldehyde and ylidic substituents mainly governs the energy differences between the enantio and diastereomeric transition states. The favourable reactivity is also explained through Fukui function calculations.
Keywords: Theoretical chemistry, Density functional calculations, Selenium ylides, Epoxidation, Enantio, Stereoselectivity, Diastereoselectivity, Fukui functions
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 10101018
Quantum
information description of reactive systems
Roman F Nalewajski
Department of Theoretical Chemistry,
Jagiellonian University, R. Ingardena 3, 30060 Cracow, Poland
Email: nalewajs@chemia.uj.edu.pl
Received
14 February 2014; accepted 12 March 2014
Information Theory (IT) of
molecular electronic states is applied to describe equilibria in separate
reactants and reactive system as a whole. It uses the resultant (quantum) measures of the information content in electronic states, determined by
both the classical (probability/density) functionals and their nonclassical
(phase/current)related complements. The intrareactant (fragment) equilibrium
state in the separate reactant is uniquely characterized by its equilibrium
phase related to its own electron distribution, while the interreactant
(molecular) equilibrium state reflects the stationary electron density of the
whole reactive system. The probability currents of the nonbonded reactants,
e.g., the isolated fragments or their mutuallyclosed analogs in the system
“promolecular” reference, and of the bonded (mutuallyopen) fragments in the
whole reactive system, are compared to identify the currentpromotion of these
subsystems. The illustrative case of the twoorbital (2electron) system is
examined in some detail to generate the combination formula for the overall
current and to identify its additive and nonadditive components. Electron
communications between reactants are examined and IT descriptors of the
multiplicity and covalent/ionic composition of chemical bonds are related to
the additive and nonadditive information contributions in local and atomic
orbital resolutions.
Keywords:
Communication systems, Current promotion of reactants, Electronic
communications in molecules, Information theory, Molecular information
channels, Probability currents, Quantum information measures, Reactive systems
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp.
10191030
Electrostatics
and tailoring for aggregation of small linear molecules:
An ab initio study
Gurmeet Singh & Shridhar R Gadre*
Department of Chemistry, Indian Institute of Technology, Kanpur 208 016, India
Email:
gadre@iitk.ac.in
Received 8 April
2014; accepted 3 May 2014
Features of
the molecular electrostatic potential (MESP) for three linear triatomic
molecules, viz., CO_{2},
CS_{2} and OCS are utilized for a
comparative study of their aggregation into small clusters. Trial structures of
clusters upto tetramers, generated by using the MESP insights, are subjected to
geometry optimization employing secondorder MøllerPlesset (MP2)_{ }theory,
with correlation consistent augccpvTZ (aTZ) basis set. Single point energies
at MP2/aQZ levels are calculated for the estimation of binding energies at
complete basis set (CBS) limit. Calculations at the coupled cluster singles and
doubles with perturbative triples (CCSD(T)) level are also reported for the
most favorable tetramers using the molecular tailoring approach (MTA).
Geometrical parameters such as rotational constants thus obtained are found to
be in good agreement with the corresponding experimental ones. Minimal nature
of the reported structures is confirmed by the vibrational frequency
calculations at MP2/aDZ level of theory. The current work offers some hints
towards the patterns in the oligomer formation for these molecules and a
comparison of the motifs found in the corresponding crystal structure is made.
Keywords: Theoretical chemistry, Ab initio calculations, Molecular clusters, Secondorder
MøllerPlesset theory, Coupled cluster singles and doubles with perturbative
triples, Molecular electrostatic potential,
Molecular tailoring approach
Indian Journal of Chemistry
Vol. 53A,
AugSept 2014, pp. 10311035
Electronic stress tensor of chemical bond
Akitomo Tachibana*
Department of Micro Engineering, Kyoto University, Kyoto 6158540, Japan
Email: akitomo@scl.kyotou.ac.jp
Received 28 March 2014; accepted 11 April 2014
Electronic stress tensor of chemical
bond is a 3dim real symmetric component of a 3dim
real stress tensor . The
complementary antisymmetric component drives the torque of electron spin through the vorticity . The
whole picture has quite recently been unified on the variation principle of
gravity using the semiclassical action integral. This theory is extended in
this paper using a quantum action integral based on a simple SUGRA
(supergravity), which is a simple SUSY (supersymmetry) model of gravity.
Keywords: Stress tensor, Electronic stress tensor, Energy
density, Semiclassical
action integral,
Quantum action integral
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 10361042
A gradientbased trust radius update
suitable for saddle point and
transition state optimization
Paul W Ayers* & Sandra Rabi
Department of Chemistry & Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1, Canada
Email: ayers@chemistry.mcmaster.ca
Received 23 April 2014; accepted 25 April 2014
A new trust radius method, appropriate for saddle point optimization is proposed. The idea is to ensure that the gradients from the quadratic model, and the exact computed gradients, are similar in direction and magnitude. For transition state optimization, the new trust radius method is found to work somewhat better than more traditional methods, based on the value of the objective function.
Keywords: Theoretical chemistry, Saddle point optimization, Transition state optimization, Trust
radius method
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 10431051
Soft
nuclear density and nuclear repulsion
Ramon CarbóDorca
Institut de Química Computacional i Catàlisi, Universitat de Girona,
Catalonia, Spain
Email: quantumqsar@hotmail.com
Received 2
April 2014; accepted 9 May 2014
This paper proposes the
description of a soft nuclear density and the associated soft nuclear Coulombic
repulsion. The idea just consists into describing soft nuclear repulsion
expressions substituting the usual pointlike nuclear charge density by means
of a Gaussian distribution. The theoretical structure and management of such an
approach is discussed.
Keywords: Theoretical chemistry,
BornOppenheimer approximation, Nuclear density, Soft nuclear density, Nuclear
repulsion, Soft nuclear repulsion
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 10521057
Polarization,
reactivity and quantum molecular capacitance: From electrostatics to density
functional theory
Patrice Delarue &
Patrick Senet*
Laboratoire Interdisciplinaire Carnot de
Bourgogne, UMR 6303 CNRSUniversité de Bourgogne, Dijon, France
Email: psenet@ubourgogne.fr
Received 31
March 2014; revised and accepted 6 May 2014
The charge distribution
induced by an inhomogeneous electric potential applied to a molecule is in fact
the sum of two terms: polarization (localized) and chemical (delocalized)
charge distributions. The chemical induced charge distribution is proportional
to the inhomogeneous response of the molecule to an electron transfer (Fukui
function). Analogy with the electrostatic Thomson theorem for the perfect
conductors permits to define the quantum molecular capacitance.
Keywords: Theoretical
chemistry, Density functional calculations, Polarization, Chemical reactivity,
Electrostatics, Quantum molecular capacitance, Fukui function
Indian Journal of Chemistry
Vol. 53A, AugSept 2014, pp. 10581063
Solvation
of graphene sheets vs. dimerization: A theoretical study
Balázs Hajgató^{a}, Songül Güryel^{a},
Yves Dauphin^{b}, JeanMarie Blairon^{b}, Gregory Van Lier^{a},
Hans E Miltner^{b}, Frank De Proft^{a} & Paul Geerlings^{a,
}*
^{a}Free University of Brussels  Vrije
Universiteit Brussel (VUB), Research Group General Chemistry (ALGC),
Pleinlaan 2, B1050 Brussels, Belgium
Email: pgeerlin@vub.ac.be
^{b}SOLVAY S.A., Innovation Center,
Ransbeekstraat 310, B1120 Brussels, Belgium
Received 6 May 2014; accepted 16 May 2014
Thermodynamic
stability of graphene against stacking in the gas phase and in different
solvents (Nmethyl2pyrrolidone), dimethyl
sulfoxide, and water) has been investigated using the semiempirical PM6 method
combined with supermolecular approach, and with Periodic Boundary Conditions using
Density Functional Theory in conjunction with the PerdewBurkeErzernhof
functional. In the case of a supermolecular approach, the effect of the ratio
of the edge and the center part on the solvation enthalpy has also been
investigated.
Keywords: Thermodynamic
stability, Graphene, Dimerization, Stacking, Solubility