The [FHCl]- molecular anion: Structural aspects, global surface, and vibrational eigenspectrum

Neil E. Klepeis, Allan L L East, A. Császár, Wesley D. Allen, Timothy J. Lee, David W. Schwenke

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The [FHCl]- molecular anion has been investigated in detail by means of state-of-the-art ab initio electronic structure methods, including restricted Hartree-Fock (RHF), Møller-Plesset perturbation theory (MP2-MP4), and coupled-cluster and Brueckner methods incorporating various degrees of excitation [CCSD, CCSD(T), BD, BD(T), and BD(TQ)]. The one-particle Gaussian basis sets ranged in quality from F[6s4p2d], Cl[10s7p2d], and H[4s2p] to F[18s13p6d4f], Cl[20s14p7d5f], and H[8s3p2d1f]. The first phase of the investigation focused on the prediction of thermochemical, spectroscopic, and bonding properties of [FHCl]- and the chemical interpretation thereof. The final proposals for the geometric structure and binding energy of the complex are re(H-F)=0.963±0.003 Å, R e(H-Cl)=1.925±0.015 Å, and D0(HF +Cl -)=21.8±0.4 kcal mol-1. A Morokuma decomposition of the ion-molecule bonding gave the following electrostatic (ES), polarization (PL), exchange repulsion (EX), dispersion (DISP), and charge-transfer plus higher-order mixing (CT+MIX) components of the vibrationless complexation energy: -27.3 (ES), -5.2 (PL), +18.3 (EX), -4.5 (DISP), and -5.0 (CT+MIX) kcal mol-1. The second phase of the work involved the construction of a CCSD global surface from 208 and 228 energy points for linear and bent conformations, respectively, these being fit to rms errors of only 3.9 and 9.3 cm-1, respectively, below 8000 cm-1. The surface was represented by a flexible analytic form which reproduces the quartic force field at equilibrium, exhibits the proper asymptotic properties, and is generally applicable to ion-molecule systems. The final phase of the study entailed the determination of converged J=0 and J=1 variational eigenstates of the [FHCl]- surface to near the HF+Cl- dissociation threshold by employing Jacobi coordinates and vibrational configuration interaction expansions in terms of natural modals. The fundamental vibrational frequencies given by the analysis were v1=247, v2=876, and v 3=2884 cm-1. The complete vibrational eigenspectrum was then analyzed in terms of several contemporary dynamical issues, including vibrational adiabaticity, anharmonic resonances, densities of high-lying states, and signatures of quantum ergodicity.

Original languageEnglish
Pages (from-to)3865-3897
Number of pages33
JournalThe Journal of Chemical Physics
Volume99
Issue number5
Publication statusPublished - 1993

Fingerprint

Anions
anions
Electrostatics
Ions
Polarization
electrostatics
thermochemical properties
asymptotic properties
Molecules
Vibrational spectra
polarization
Complexation
Binding energy
field theory (physics)
configuration interaction
Electronic structure
Conformations
energy
proposals
Charge transfer

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Klepeis, N. E., East, A. L. L., Császár, A., Allen, W. D., Lee, T. J., & Schwenke, D. W. (1993). The [FHCl]- molecular anion: Structural aspects, global surface, and vibrational eigenspectrum. The Journal of Chemical Physics, 99(5), 3865-3897.

The [FHCl]- molecular anion : Structural aspects, global surface, and vibrational eigenspectrum. / Klepeis, Neil E.; East, Allan L L; Császár, A.; Allen, Wesley D.; Lee, Timothy J.; Schwenke, David W.

In: The Journal of Chemical Physics, Vol. 99, No. 5, 1993, p. 3865-3897.

Research output: Contribution to journalArticle

Klepeis, NE, East, ALL, Császár, A, Allen, WD, Lee, TJ & Schwenke, DW 1993, 'The [FHCl]- molecular anion: Structural aspects, global surface, and vibrational eigenspectrum', The Journal of Chemical Physics, vol. 99, no. 5, pp. 3865-3897.
Klepeis, Neil E. ; East, Allan L L ; Császár, A. ; Allen, Wesley D. ; Lee, Timothy J. ; Schwenke, David W. / The [FHCl]- molecular anion : Structural aspects, global surface, and vibrational eigenspectrum. In: The Journal of Chemical Physics. 1993 ; Vol. 99, No. 5. pp. 3865-3897.
@article{55151028bc424872bcf519e56b5ab7b2,
title = "The [FHCl]- molecular anion: Structural aspects, global surface, and vibrational eigenspectrum",
abstract = "The [FHCl]- molecular anion has been investigated in detail by means of state-of-the-art ab initio electronic structure methods, including restricted Hartree-Fock (RHF), M{\o}ller-Plesset perturbation theory (MP2-MP4), and coupled-cluster and Brueckner methods incorporating various degrees of excitation [CCSD, CCSD(T), BD, BD(T), and BD(TQ)]. The one-particle Gaussian basis sets ranged in quality from F[6s4p2d], Cl[10s7p2d], and H[4s2p] to F[18s13p6d4f], Cl[20s14p7d5f], and H[8s3p2d1f]. The first phase of the investigation focused on the prediction of thermochemical, spectroscopic, and bonding properties of [FHCl]- and the chemical interpretation thereof. The final proposals for the geometric structure and binding energy of the complex are re(H-F)=0.963±0.003 {\AA}, R e(H-Cl)=1.925±0.015 {\AA}, and D0(HF +Cl -)=21.8±0.4 kcal mol-1. A Morokuma decomposition of the ion-molecule bonding gave the following electrostatic (ES), polarization (PL), exchange repulsion (EX), dispersion (DISP), and charge-transfer plus higher-order mixing (CT+MIX) components of the vibrationless complexation energy: -27.3 (ES), -5.2 (PL), +18.3 (EX), -4.5 (DISP), and -5.0 (CT+MIX) kcal mol-1. The second phase of the work involved the construction of a CCSD global surface from 208 and 228 energy points for linear and bent conformations, respectively, these being fit to rms errors of only 3.9 and 9.3 cm-1, respectively, below 8000 cm-1. The surface was represented by a flexible analytic form which reproduces the quartic force field at equilibrium, exhibits the proper asymptotic properties, and is generally applicable to ion-molecule systems. The final phase of the study entailed the determination of converged J=0 and J=1 variational eigenstates of the [FHCl]- surface to near the HF+Cl- dissociation threshold by employing Jacobi coordinates and vibrational configuration interaction expansions in terms of natural modals. The fundamental vibrational frequencies given by the analysis were v1=247, v2=876, and v 3=2884 cm-1. The complete vibrational eigenspectrum was then analyzed in terms of several contemporary dynamical issues, including vibrational adiabaticity, anharmonic resonances, densities of high-lying states, and signatures of quantum ergodicity.",
author = "Klepeis, {Neil E.} and East, {Allan L L} and A. Cs{\'a}sz{\'a}r and Allen, {Wesley D.} and Lee, {Timothy J.} and Schwenke, {David W.}",
year = "1993",
language = "English",
volume = "99",
pages = "3865--3897",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "5",

}

TY - JOUR

T1 - The [FHCl]- molecular anion

T2 - Structural aspects, global surface, and vibrational eigenspectrum

AU - Klepeis, Neil E.

AU - East, Allan L L

AU - Császár, A.

AU - Allen, Wesley D.

AU - Lee, Timothy J.

AU - Schwenke, David W.

PY - 1993

Y1 - 1993

N2 - The [FHCl]- molecular anion has been investigated in detail by means of state-of-the-art ab initio electronic structure methods, including restricted Hartree-Fock (RHF), Møller-Plesset perturbation theory (MP2-MP4), and coupled-cluster and Brueckner methods incorporating various degrees of excitation [CCSD, CCSD(T), BD, BD(T), and BD(TQ)]. The one-particle Gaussian basis sets ranged in quality from F[6s4p2d], Cl[10s7p2d], and H[4s2p] to F[18s13p6d4f], Cl[20s14p7d5f], and H[8s3p2d1f]. The first phase of the investigation focused on the prediction of thermochemical, spectroscopic, and bonding properties of [FHCl]- and the chemical interpretation thereof. The final proposals for the geometric structure and binding energy of the complex are re(H-F)=0.963±0.003 Å, R e(H-Cl)=1.925±0.015 Å, and D0(HF +Cl -)=21.8±0.4 kcal mol-1. A Morokuma decomposition of the ion-molecule bonding gave the following electrostatic (ES), polarization (PL), exchange repulsion (EX), dispersion (DISP), and charge-transfer plus higher-order mixing (CT+MIX) components of the vibrationless complexation energy: -27.3 (ES), -5.2 (PL), +18.3 (EX), -4.5 (DISP), and -5.0 (CT+MIX) kcal mol-1. The second phase of the work involved the construction of a CCSD global surface from 208 and 228 energy points for linear and bent conformations, respectively, these being fit to rms errors of only 3.9 and 9.3 cm-1, respectively, below 8000 cm-1. The surface was represented by a flexible analytic form which reproduces the quartic force field at equilibrium, exhibits the proper asymptotic properties, and is generally applicable to ion-molecule systems. The final phase of the study entailed the determination of converged J=0 and J=1 variational eigenstates of the [FHCl]- surface to near the HF+Cl- dissociation threshold by employing Jacobi coordinates and vibrational configuration interaction expansions in terms of natural modals. The fundamental vibrational frequencies given by the analysis were v1=247, v2=876, and v 3=2884 cm-1. The complete vibrational eigenspectrum was then analyzed in terms of several contemporary dynamical issues, including vibrational adiabaticity, anharmonic resonances, densities of high-lying states, and signatures of quantum ergodicity.

AB - The [FHCl]- molecular anion has been investigated in detail by means of state-of-the-art ab initio electronic structure methods, including restricted Hartree-Fock (RHF), Møller-Plesset perturbation theory (MP2-MP4), and coupled-cluster and Brueckner methods incorporating various degrees of excitation [CCSD, CCSD(T), BD, BD(T), and BD(TQ)]. The one-particle Gaussian basis sets ranged in quality from F[6s4p2d], Cl[10s7p2d], and H[4s2p] to F[18s13p6d4f], Cl[20s14p7d5f], and H[8s3p2d1f]. The first phase of the investigation focused on the prediction of thermochemical, spectroscopic, and bonding properties of [FHCl]- and the chemical interpretation thereof. The final proposals for the geometric structure and binding energy of the complex are re(H-F)=0.963±0.003 Å, R e(H-Cl)=1.925±0.015 Å, and D0(HF +Cl -)=21.8±0.4 kcal mol-1. A Morokuma decomposition of the ion-molecule bonding gave the following electrostatic (ES), polarization (PL), exchange repulsion (EX), dispersion (DISP), and charge-transfer plus higher-order mixing (CT+MIX) components of the vibrationless complexation energy: -27.3 (ES), -5.2 (PL), +18.3 (EX), -4.5 (DISP), and -5.0 (CT+MIX) kcal mol-1. The second phase of the work involved the construction of a CCSD global surface from 208 and 228 energy points for linear and bent conformations, respectively, these being fit to rms errors of only 3.9 and 9.3 cm-1, respectively, below 8000 cm-1. The surface was represented by a flexible analytic form which reproduces the quartic force field at equilibrium, exhibits the proper asymptotic properties, and is generally applicable to ion-molecule systems. The final phase of the study entailed the determination of converged J=0 and J=1 variational eigenstates of the [FHCl]- surface to near the HF+Cl- dissociation threshold by employing Jacobi coordinates and vibrational configuration interaction expansions in terms of natural modals. The fundamental vibrational frequencies given by the analysis were v1=247, v2=876, and v 3=2884 cm-1. The complete vibrational eigenspectrum was then analyzed in terms of several contemporary dynamical issues, including vibrational adiabaticity, anharmonic resonances, densities of high-lying states, and signatures of quantum ergodicity.

UR - http://www.scopus.com/inward/record.url?scp=0007747711&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0007747711&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0007747711

VL - 99

SP - 3865

EP - 3897

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 5

ER -