On the choice of coordinates in anharmonic theoretical vibrational spectroscopy: Harmonic vs. anharmonic coupling in vibrational configuration interaction

The Journal of Chemical Physics
Paweł T PanekChristoph R Jacob

Abstract

By a suitable choice of coordinates, the computational effort required for calculations of anharmonic vibrational spectra can be reduced significantly. By using suitable localized-mode coordinates obtained from an orthogonal transformation of the conventionally used normal-mode coordinates, anharmonic couplings between modes can be significantly reduced. However, such a transformation introduces harmonic couplings between the localized modes. To elucidate the role of these harmonic couplings, we consider the vibrational self-consistent field (VSCF)/vibrational configuration interaction (VCI) calculations for both few-mode model systems and for ethene as a molecular test case. We show that large harmonic couplings can result in significant errors in localized-mode L-VSCF/L-VCI calculations and study the convergence with respect to the size of the VCI excitation space. To further elucidate the errors introduced by harmonic couplings, we discuss the connection between L-VSCF/L-VCI and vibrational exciton models. With the help of our results, we propose an algorithm for the localization of normal modes in suitable subsets that are chosen to strictly limit the errors introduced by the harmonic couplings while still leading to maxima...Continue Reading

References

May 2, 2002·Journal of Computational Chemistry·Johannes NeugebauerBernd A Hess
Oct 22, 2005·Physical Chemistry Chemical Physics : PCCP·Tomica HrenarGuntram Rauhut
Sep 1, 2006·The Journal of Chemical Physics·Thomas la Cour JansenJasper Knoester
Jun 8, 2007·The Journal of Chemical Physics·Peter Seidler, Ove Christiansen
Nov 6, 2007·The Journal of Chemical Physics·Yohann Scribano, David M Benoit
Mar 28, 2008·Chemical Reviews·Minhaeng Cho
Mar 5, 2009·The Journal of Chemical Physics·Christoph R Jacob, Markus Reiher
Apr 14, 2009·The Journal of Physical Chemistry. B·Christoph R JacobMarkus Reiher
Oct 2, 2009·The Journal of Chemical Physics·Michael Neff, Guntram Rauhut
Nov 13, 2009·Chemistry : a European Journal·Christoph R JacobMarkus Reiher
Sep 14, 2010·The Journal of Chemical Physics·Yohann ScribanoDavid M Benoit
Feb 10, 2011·The Journal of Chemical Physics·Peter SeidlerOve Christiansen
Oct 15, 2011·Physical Chemistry Chemical Physics : PCCP·Attila G CsászárGábor Czakó
Nov 5, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Christoph R Jacob
Dec 5, 2012·The Journal of Chemical Physics·Kiyoshi YagiSo Hirata
Feb 8, 2013·The Journal of Chemical Physics·Florian PfeifferKirk A Peterson
Mar 27, 2013·The Journal of Physical Chemistry. a·Sandra Luber
Dec 11, 2013·The Journal of Chemical Physics·Wataru Mizukami, David P Tew
Feb 18, 2014·The Journal of Chemical Physics·Florian Pfeiffer, Guntram Rauhut
Jul 2, 2014·Physical Chemistry Chemical Physics : PCCP·Dominik Oschetzki, Guntram Rauhut
Aug 1, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Paweł T Panek, Christoph R Jacob
Sep 15, 2014·The Journal of Chemical Physics·Xiaolu Cheng, Ryan P Steele
Apr 17, 2015·The Journal of Chemical Physics·Carolin König, Ove Christiansen
Apr 22, 2015·Accounts of Chemical Research·Vincenzo BaroneCristina Puzzarini
Oct 9, 2015·The Journal of Physical Chemistry. a·Emil Lund KlintingOve Christiansen
Oct 10, 2015·The Journal of Chemical Physics·Jacob A Faucheaux, So Hirata
Nov 18, 2015·Journal of Chemical Theory and Computation·Alberto BaiardiVincenzo Barone
Feb 26, 2016·Journal of Chemical Theory and Computation·Paul M Zimmerman, Peter Smereka
Apr 3, 2016·The Journal of Chemical Physics·Andrew MolinaPaul M Zimmerman
May 2, 2016·The Journal of Chemical Physics·Paweł T Panek, Christoph R Jacob
Jun 3, 2016·The Journal of Chemical Physics·Magnus W D Hanson-Heine
Jun 28, 2016·Journal of Chemical Theory and Computation·Ana V CunhaThomas L C Jansen
Jun 29, 2016·The Journal of Physical Chemistry. a·Aleksandr Y PereverzevOleg V Boyarkin
Jul 30, 2016·The Journal of Physical Chemistry Letters·Paweł T Panek, Christoph R Jacob
Oct 27, 2016·The Journal of Chemical Physics·Xiaolu ChengRyan P Steele
Nov 22, 2016·Journal of Computational Chemistry·Fouad S HusseiniJonathan D Hirst
Jul 6, 2017·Journal of Chemical Theory and Computation·Alberto BaiardiMarkus Reiher

❮ Previous
Next ❯

Citations

Mar 10, 2021·The Journal of Chemical Physics·Tina Mathea, Guntram Rauhut

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Hereditary Sensory Autonomic Neuropathy

Hereditary Sensory Autonomic Neuropathies are a group of inherited neurodegenerative disorders characterized clinically by loss of sensation and autonomic dysfunction. Here is the latest research on these neuropathies.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Landau-Kleffner Syndrome

Landau Kleffner syndrome (LKS), also called infantile acquired aphasia, acquired epileptic aphasia, or aphasia with convulsive disorder, is a rare childhood neurological syndrome characterized by the sudden or gradual development of aphasia (the inability to understand or express language) and an abnormal electroencephalogram. Discover the latest research on LKS here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.

Regulation of Vocal-Motor Plasticity

Dopaminergic projections to the basal ganglia and nucleus accumbens shape the learning and plasticity of motivated behaviors across species including the regulation of vocal-motor plasticity and performance in songbirds. Discover the latest research on the regulation of vocal-motor plasticity here.