Polarizability, hardness and electrophilicity as global descriptors for intramolecular proton transfer reaction path

Sankarlal Ash, Hasibul Beg, Prativa Mazumdar, Guillermo Salgado-Morán, Ajay Misra

Resultado de la investigación: Article

5 Citas (Scopus)

Resumen

Potential energy (PE) curves for intramolecular proton transfer in the ground (GSIPT) and excited (ESIPT) states of 1-hydroxy-2-acetonaphthone (1H2AN) is studied using DFT-B3LYP/6-31+G(d,p) and TD-DFT/6-31+G(d,p) level of theory respectively. Our calculations suggest the non-viability of ground state intramolecular proton transfer in 1H2AN. Excited states PE calculations support the viability of ESIPT process in 1H2AN. Here, for the first time, polarizability, chemical hardness and electrophilicity are being used as global reactivity descriptors to locate the transition state for intermolecular proton transfer process. Both the minimum polarizability principle (MPP) and maximum hardness principle (MHP) are being obeyed along the intrinsic reaction co-ordinate (IRC) for intramolecular proton transfer process. We have also raised the decade old issue i.e. the use of O-H distance of enol tautomer as proton transfer co-ordinate instead of IRC. Our computation of these global reactivity descriptors along the proton transfer co-ordinate support intrinsic reaction coordinate (IRC) as the effective proton transfer co-ordinate, instead of variation of O-H distance of enol tautomer.

Idioma originalEnglish
Páginas (desde-hasta)50-55
Número de páginas6
PublicaciónComputational and Theoretical Chemistry
Volumen1031
DOI
EstadoPublished - 1 mar 2014

Huella dactilar

Proton transfer
Hardness
Protons
hardness
protons
tautomers
Potential energy
Excited states
Discrete Fourier transforms
reactivity
potential energy
viability
Ground state
excitation
Hydrogen
ground state
curves
1'-hydroxy-2'-acetonaphthone

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

Ash, Sankarlal ; Beg, Hasibul ; Mazumdar, Prativa ; Salgado-Morán, Guillermo ; Misra, Ajay. / Polarizability, hardness and electrophilicity as global descriptors for intramolecular proton transfer reaction path. En: Computational and Theoretical Chemistry. 2014 ; Vol. 1031. pp. 50-55.
@article{984db7268cca43ab8399fe9986b4fee8,
title = "Polarizability, hardness and electrophilicity as global descriptors for intramolecular proton transfer reaction path",
abstract = "Potential energy (PE) curves for intramolecular proton transfer in the ground (GSIPT) and excited (ESIPT) states of 1-hydroxy-2-acetonaphthone (1H2AN) is studied using DFT-B3LYP/6-31+G(d,p) and TD-DFT/6-31+G(d,p) level of theory respectively. Our calculations suggest the non-viability of ground state intramolecular proton transfer in 1H2AN. Excited states PE calculations support the viability of ESIPT process in 1H2AN. Here, for the first time, polarizability, chemical hardness and electrophilicity are being used as global reactivity descriptors to locate the transition state for intermolecular proton transfer process. Both the minimum polarizability principle (MPP) and maximum hardness principle (MHP) are being obeyed along the intrinsic reaction co-ordinate (IRC) for intramolecular proton transfer process. We have also raised the decade old issue i.e. the use of O-H distance of enol tautomer as proton transfer co-ordinate instead of IRC. Our computation of these global reactivity descriptors along the proton transfer co-ordinate support intrinsic reaction coordinate (IRC) as the effective proton transfer co-ordinate, instead of variation of O-H distance of enol tautomer.",
keywords = "Chemical hardness, Chemical potential, DFT, Electrophilicity index, Polarizability, Proton transfer",
author = "Sankarlal Ash and Hasibul Beg and Prativa Mazumdar and Guillermo Salgado-Mor{\'a}n and Ajay Misra",
year = "2014",
month = "3",
day = "1",
doi = "10.1016/j.comptc.2014.01.010",
language = "English",
volume = "1031",
pages = "50--55",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",

}

Polarizability, hardness and electrophilicity as global descriptors for intramolecular proton transfer reaction path. / Ash, Sankarlal; Beg, Hasibul; Mazumdar, Prativa; Salgado-Morán, Guillermo; Misra, Ajay.

En: Computational and Theoretical Chemistry, Vol. 1031, 01.03.2014, p. 50-55.

Resultado de la investigación: Article

TY - JOUR

T1 - Polarizability, hardness and electrophilicity as global descriptors for intramolecular proton transfer reaction path

AU - Ash, Sankarlal

AU - Beg, Hasibul

AU - Mazumdar, Prativa

AU - Salgado-Morán, Guillermo

AU - Misra, Ajay

PY - 2014/3/1

Y1 - 2014/3/1

N2 - Potential energy (PE) curves for intramolecular proton transfer in the ground (GSIPT) and excited (ESIPT) states of 1-hydroxy-2-acetonaphthone (1H2AN) is studied using DFT-B3LYP/6-31+G(d,p) and TD-DFT/6-31+G(d,p) level of theory respectively. Our calculations suggest the non-viability of ground state intramolecular proton transfer in 1H2AN. Excited states PE calculations support the viability of ESIPT process in 1H2AN. Here, for the first time, polarizability, chemical hardness and electrophilicity are being used as global reactivity descriptors to locate the transition state for intermolecular proton transfer process. Both the minimum polarizability principle (MPP) and maximum hardness principle (MHP) are being obeyed along the intrinsic reaction co-ordinate (IRC) for intramolecular proton transfer process. We have also raised the decade old issue i.e. the use of O-H distance of enol tautomer as proton transfer co-ordinate instead of IRC. Our computation of these global reactivity descriptors along the proton transfer co-ordinate support intrinsic reaction coordinate (IRC) as the effective proton transfer co-ordinate, instead of variation of O-H distance of enol tautomer.

AB - Potential energy (PE) curves for intramolecular proton transfer in the ground (GSIPT) and excited (ESIPT) states of 1-hydroxy-2-acetonaphthone (1H2AN) is studied using DFT-B3LYP/6-31+G(d,p) and TD-DFT/6-31+G(d,p) level of theory respectively. Our calculations suggest the non-viability of ground state intramolecular proton transfer in 1H2AN. Excited states PE calculations support the viability of ESIPT process in 1H2AN. Here, for the first time, polarizability, chemical hardness and electrophilicity are being used as global reactivity descriptors to locate the transition state for intermolecular proton transfer process. Both the minimum polarizability principle (MPP) and maximum hardness principle (MHP) are being obeyed along the intrinsic reaction co-ordinate (IRC) for intramolecular proton transfer process. We have also raised the decade old issue i.e. the use of O-H distance of enol tautomer as proton transfer co-ordinate instead of IRC. Our computation of these global reactivity descriptors along the proton transfer co-ordinate support intrinsic reaction coordinate (IRC) as the effective proton transfer co-ordinate, instead of variation of O-H distance of enol tautomer.

KW - Chemical hardness

KW - Chemical potential

KW - DFT

KW - Electrophilicity index

KW - Polarizability

KW - Proton transfer

UR - http://www.scopus.com/inward/record.url?scp=84893486046&partnerID=8YFLogxK

U2 - 10.1016/j.comptc.2014.01.010

DO - 10.1016/j.comptc.2014.01.010

M3 - Article

AN - SCOPUS:84893486046

VL - 1031

SP - 50

EP - 55

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

ER -