The methylene saga continues: Stretching fundamentals and zero-point energy of X̃3 B1 CH2

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The vibrational fundamentals and the rotational levels up to J=7 of the X̃3B1 and ã1A1 electronic states of CH2 have been computed completely ab initio. The calculations were based on converged, variational nuclear motion calculations employing high-quality ab initio quartic force field approximations of the related potential energy surfaces (PES). The vibrational fundamentals obtained are compared to other computational results, namely those obtained from second-order vibrational perturbation theory (VPT2) and the nonrigid-rotation- large-amplitude-internal-motion Hamiltonian (NRLH) approach. The variationally computed rotational transitions are compared both to experimentally available results and to results obtained using empirical, fitted PESs. The comparisons suggest that while the fitted PESs of X̃3B1 CH 2 reproduce excellently the available rovibrational transition wavenumbers, the corresponding stretching fundamental term values, which have not been determined experimentally, are less accurate than the ab initio values obtained in the present study. This means that the zero-point energy (ZPE) computed ab initio in the present work is an improvement over that computed from the fitted PES of X̃3B1 CH2. No similar problems are observed for the semirigid ã1A1 state of CH2, where the computed, the fitted, and the experimental results all agree with each other. The symmetric and antisymmetric stretching fundamentals of X̃3B1 CH2 obtained in this study are 3035±7 and 3249±7 cm-1, respectively. The corresponding ZPE of X̃3B1 is 3733±10 cm -1, while that of ã1A1 CH2 is 3605±15 cm-1.

Original languageEnglish
Pages (from-to)283-294
Number of pages12
JournalJournal of Molecular Structure
Volume780-781
Issue numberSPEC. ISS.
DOIs
Publication statusPublished - Jan 3 2006

Fingerprint

Potential energy surfaces
zero point energy
methylene
Stretching
potential energy
Hamiltonians
Electronic states
field theory (physics)
perturbation theory
methylidyne
approximation
electronics

Keywords

  • Ab initio calculations
  • Nuclear motion calculations
  • Rotational transitions
  • Stretching fundamentals
  • X̃ B and ãA methylene (CH)
  • Zero-point energy

ASJC Scopus subject areas

  • Structural Biology
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics
  • Materials Science (miscellaneous)

Cite this

The methylene saga continues : Stretching fundamentals and zero-point energy of X̃3 B1 CH2. / Furtenbacher, T.; Czakó, G.; Sutcliffe, Brian T.; Császár, A.; Szalay, V.

In: Journal of Molecular Structure, Vol. 780-781, No. SPEC. ISS., 03.01.2006, p. 283-294.

Research output: Contribution to journalArticle

@article{665006a48eaa4cd8b0e4aac4456b8e82,
title = "The methylene saga continues: Stretching fundamentals and zero-point energy of X̃3 B1 CH2",
abstract = "The vibrational fundamentals and the rotational levels up to J=7 of the X̃3B1 and {\~a}1A1 electronic states of CH2 have been computed completely ab initio. The calculations were based on converged, variational nuclear motion calculations employing high-quality ab initio quartic force field approximations of the related potential energy surfaces (PES). The vibrational fundamentals obtained are compared to other computational results, namely those obtained from second-order vibrational perturbation theory (VPT2) and the nonrigid-rotation- large-amplitude-internal-motion Hamiltonian (NRLH) approach. The variationally computed rotational transitions are compared both to experimentally available results and to results obtained using empirical, fitted PESs. The comparisons suggest that while the fitted PESs of X̃3B1 CH 2 reproduce excellently the available rovibrational transition wavenumbers, the corresponding stretching fundamental term values, which have not been determined experimentally, are less accurate than the ab initio values obtained in the present study. This means that the zero-point energy (ZPE) computed ab initio in the present work is an improvement over that computed from the fitted PES of X̃3B1 CH2. No similar problems are observed for the semirigid {\~a}1A1 state of CH2, where the computed, the fitted, and the experimental results all agree with each other. The symmetric and antisymmetric stretching fundamentals of X̃3B1 CH2 obtained in this study are 3035±7 and 3249±7 cm-1, respectively. The corresponding ZPE of X̃3B1 is 3733±10 cm -1, while that of {\~a}1A1 CH2 is 3605±15 cm-1.",
keywords = "Ab initio calculations, Nuclear motion calculations, Rotational transitions, Stretching fundamentals, X̃ B and {\~a}A methylene (CH), Zero-point energy",
author = "T. Furtenbacher and G. Czak{\'o} and Sutcliffe, {Brian T.} and A. Cs{\'a}sz{\'a}r and V. Szalay",
year = "2006",
month = "1",
day = "3",
doi = "10.1016/j.molstruc.2005.06.052",
language = "English",
volume = "780-781",
pages = "283--294",
journal = "Journal of Molecular Structure",
issn = "0022-2860",
publisher = "Elsevier",
number = "SPEC. ISS.",

}

TY - JOUR

T1 - The methylene saga continues

T2 - Stretching fundamentals and zero-point energy of X̃3 B1 CH2

AU - Furtenbacher, T.

AU - Czakó, G.

AU - Sutcliffe, Brian T.

AU - Császár, A.

AU - Szalay, V.

PY - 2006/1/3

Y1 - 2006/1/3

N2 - The vibrational fundamentals and the rotational levels up to J=7 of the X̃3B1 and ã1A1 electronic states of CH2 have been computed completely ab initio. The calculations were based on converged, variational nuclear motion calculations employing high-quality ab initio quartic force field approximations of the related potential energy surfaces (PES). The vibrational fundamentals obtained are compared to other computational results, namely those obtained from second-order vibrational perturbation theory (VPT2) and the nonrigid-rotation- large-amplitude-internal-motion Hamiltonian (NRLH) approach. The variationally computed rotational transitions are compared both to experimentally available results and to results obtained using empirical, fitted PESs. The comparisons suggest that while the fitted PESs of X̃3B1 CH 2 reproduce excellently the available rovibrational transition wavenumbers, the corresponding stretching fundamental term values, which have not been determined experimentally, are less accurate than the ab initio values obtained in the present study. This means that the zero-point energy (ZPE) computed ab initio in the present work is an improvement over that computed from the fitted PES of X̃3B1 CH2. No similar problems are observed for the semirigid ã1A1 state of CH2, where the computed, the fitted, and the experimental results all agree with each other. The symmetric and antisymmetric stretching fundamentals of X̃3B1 CH2 obtained in this study are 3035±7 and 3249±7 cm-1, respectively. The corresponding ZPE of X̃3B1 is 3733±10 cm -1, while that of ã1A1 CH2 is 3605±15 cm-1.

AB - The vibrational fundamentals and the rotational levels up to J=7 of the X̃3B1 and ã1A1 electronic states of CH2 have been computed completely ab initio. The calculations were based on converged, variational nuclear motion calculations employing high-quality ab initio quartic force field approximations of the related potential energy surfaces (PES). The vibrational fundamentals obtained are compared to other computational results, namely those obtained from second-order vibrational perturbation theory (VPT2) and the nonrigid-rotation- large-amplitude-internal-motion Hamiltonian (NRLH) approach. The variationally computed rotational transitions are compared both to experimentally available results and to results obtained using empirical, fitted PESs. The comparisons suggest that while the fitted PESs of X̃3B1 CH 2 reproduce excellently the available rovibrational transition wavenumbers, the corresponding stretching fundamental term values, which have not been determined experimentally, are less accurate than the ab initio values obtained in the present study. This means that the zero-point energy (ZPE) computed ab initio in the present work is an improvement over that computed from the fitted PES of X̃3B1 CH2. No similar problems are observed for the semirigid ã1A1 state of CH2, where the computed, the fitted, and the experimental results all agree with each other. The symmetric and antisymmetric stretching fundamentals of X̃3B1 CH2 obtained in this study are 3035±7 and 3249±7 cm-1, respectively. The corresponding ZPE of X̃3B1 is 3733±10 cm -1, while that of ã1A1 CH2 is 3605±15 cm-1.

KW - Ab initio calculations

KW - Nuclear motion calculations

KW - Rotational transitions

KW - Stretching fundamentals

KW - X̃ B and ãA methylene (CH)

KW - Zero-point energy

UR - http://www.scopus.com/inward/record.url?scp=29644443641&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=29644443641&partnerID=8YFLogxK

U2 - 10.1016/j.molstruc.2005.06.052

DO - 10.1016/j.molstruc.2005.06.052

M3 - Article

AN - SCOPUS:29644443641

VL - 780-781

SP - 283

EP - 294

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

SN - 0022-2860

IS - SPEC. ISS.

ER -