Spectroscopic properties of HOCO and CHNO family from ab initio CCSD(T) studies

Abstract : New analytical CCSD(T)/(aug)-cc-pVQZ potential energy surfaces for HOCO and several members of the CHNO family in their electronic ground state have beendeveloped. Numerically exact rotation-vibration calculations are carried out using computational strategies based on the discrete variable representation [DVR6] and the combined functional - pointwise coordinate representations [DVR(+R)+FBR] in conjunction with contraction schemes resulting from several diagonalization and truncation steps. Several adiabatic projection schemes are employed to characterize the rovibrational levels and to study the relevance of the intermode coupling (vibrational and rovibrational mixing). Rotational constants computed for the ground vibrational state of trans-HOCO and cis-HOCO are in good agreement with the experimental values. Numerically exact vibrational transitions are also presented for the quartic force fields developed by Fortenberry et al. for trans-HOCO, cis-HOCO, and the cis-HOCO anion. Our results help to clear up a large discrepancy between vibrational perturbation theory (VPT) and vibrational configuration interaction (VCI) predictions reported for the torsional frequency by these authors. Several important spectroscopic and dynamical issues regarding quasilinear behaviour of the CHNO family are discussed.
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Poster communications
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https://hal-upec-upem.archives-ouvertes.fr/hal-00840032
Contributor : Mirjana Mladenovic <>
Submitted on : Monday, July 1, 2013 - 2:02:11 PM
Last modification on : Wednesday, September 4, 2019 - 1:52:13 PM

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  • HAL Id : hal-00840032, version 1

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M. Mladenovic. Spectroscopic properties of HOCO and CHNO family from ab initio CCSD(T) studies. 112th Bunsentagung (Annual German Conference on Physical Chemistry), May 2013, Germany. pp.1, 2013. ⟨hal-00840032⟩

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