Comparing the accuracy of perturbative and variational calculations for predicting fundamental vibrational frequencies of dihalomethanes
Three dihalogenated methane derivatives (CH F , CH FCl, and CH Cl ) were used as model systems to compare and assess the accuracy of two different approaches for predicting observed fundamental frequencies: canonical operator Van Vleck vibrational perturbation theory (CVPT) and vibrational configura...
Saved in:
Published in | The Journal of chemical physics Vol. 148; no. 8; p. 084102 |
---|---|
Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
United States
28.02.2018
|
Online Access | Get more information |
Cover
Loading…
Abstract | Three dihalogenated methane derivatives (CH
F
, CH
FCl, and CH
Cl
) were used as model systems to compare and assess the accuracy of two different approaches for predicting observed fundamental frequencies: canonical operator Van Vleck vibrational perturbation theory (CVPT) and vibrational configuration interaction (VCI). For convenience and consistency, both methods employ the Watson Hamiltonian in rectilinear normal coordinates, expanding the potential energy surface (PES) as a Taylor series about equilibrium and constructing the wavefunction from a harmonic oscillator product basis. At the highest levels of theory considered here, fourth-order CVPT and VCI in a harmonic oscillator basis with up to 10 quanta of vibrational excitation in conjunction with a 4-mode representation sextic force field (SFF-4MR) computed at MP2/cc-pVTZ with replacement CCSD(T)/aug-cc-pVQZ harmonic force constants, the agreement between computed fundamentals is closer to 0.3 cm
on average, with a maximum difference of 1.7 cm
. The major remaining accuracy-limiting factors are the accuracy of the underlying electronic structure model, followed by the incompleteness of the PES expansion. Nonetheless, computed and experimental fundamentals agree to within 5 cm
, with an average difference of 2 cm
, confirming the utility and accuracy of both theoretical models. One exception to this rule is the formally IR-inactive but weakly allowed through Coriolis-coupling H-C-H out-of-plane twisting mode of dichloromethane, whose spectrum we therefore revisit and reassign. We also investigate convergence with respect to order of CVPT, VCI excitation level, and order of PES expansion, concluding that premature truncation substantially decreases accuracy, although VCI(6)/SFF-4MR results are still of acceptable accuracy, and some error cancellation is observed with CVPT2 using a quartic force field. |
---|---|
AbstractList | Three dihalogenated methane derivatives (CH
F
, CH
FCl, and CH
Cl
) were used as model systems to compare and assess the accuracy of two different approaches for predicting observed fundamental frequencies: canonical operator Van Vleck vibrational perturbation theory (CVPT) and vibrational configuration interaction (VCI). For convenience and consistency, both methods employ the Watson Hamiltonian in rectilinear normal coordinates, expanding the potential energy surface (PES) as a Taylor series about equilibrium and constructing the wavefunction from a harmonic oscillator product basis. At the highest levels of theory considered here, fourth-order CVPT and VCI in a harmonic oscillator basis with up to 10 quanta of vibrational excitation in conjunction with a 4-mode representation sextic force field (SFF-4MR) computed at MP2/cc-pVTZ with replacement CCSD(T)/aug-cc-pVQZ harmonic force constants, the agreement between computed fundamentals is closer to 0.3 cm
on average, with a maximum difference of 1.7 cm
. The major remaining accuracy-limiting factors are the accuracy of the underlying electronic structure model, followed by the incompleteness of the PES expansion. Nonetheless, computed and experimental fundamentals agree to within 5 cm
, with an average difference of 2 cm
, confirming the utility and accuracy of both theoretical models. One exception to this rule is the formally IR-inactive but weakly allowed through Coriolis-coupling H-C-H out-of-plane twisting mode of dichloromethane, whose spectrum we therefore revisit and reassign. We also investigate convergence with respect to order of CVPT, VCI excitation level, and order of PES expansion, concluding that premature truncation substantially decreases accuracy, although VCI(6)/SFF-4MR results are still of acceptable accuracy, and some error cancellation is observed with CVPT2 using a quartic force field. |
Author | Craig, Norman C Krasnoshchekov, Sergey V Sibaev, Marat Crittenden, Deborah L Schutski, Roman S |
Author_xml | – sequence: 1 givenname: Sergey V orcidid: 000000032562500X surname: Krasnoshchekov fullname: Krasnoshchekov, Sergey V organization: Department of Chemistry, Lomonosov Moscow State University, Leninskiye Gory 1-3, Moscow 119991, Russian Federation – sequence: 2 givenname: Roman S orcidid: 0000000316543336 surname: Schutski fullname: Schutski, Roman S organization: Department of Chemistry, Rice University, Houston, Texas 77005, USA – sequence: 3 givenname: Norman C orcidid: 0000000328641910 surname: Craig fullname: Craig, Norman C organization: Department of Chemistry and Biochemistry, Oberlin College, Oberlin, Ohio 44074, USA – sequence: 4 givenname: Marat orcidid: 0000000276234992 surname: Sibaev fullname: Sibaev, Marat organization: Research School of Chemistry, Australian National University, Canberra, ACT 2601, Australia – sequence: 5 givenname: Deborah L surname: Crittenden fullname: Crittenden, Deborah L organization: Department of Chemistry, University of Canterbury, Christchurch 8140, New Zealand |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/29495771$$D View this record in MEDLINE/PubMed |
BookMark | eNo1kEtOwzAYhC0Eog9YcAHkC6T4GcdLVPGSKrGBdeXYv6lR4gTHqdQbcGxSoKvRaGa-xSzQeewiIHRDyYqSkt_RlSSMMC3P0JySSheq1GSGFsPwSQihiolLNGNaaKkUnaPvddf2JoX4gfMOsLF2TMYecOdxDymPqTY57KcgOryfepPrommwNY0dm183YN8l3CdwweYjyI_RmRZinnr7UKfTxif4GiHaAMOR78LONF0LeWciDFfowptmgOt_XaL3x4e39XOxeX16Wd9vCsulzEWlKsGoVdpw5WvN69JyDYJJXhkHJQglmLaceyJAMkOp17IGp1XpK1Y7wZbo9o_bj3ULbtun0Jp02J4uYT8a1GXQ |
CitedBy_id | crossref_primary_10_1039_D0CP03515G crossref_primary_10_1134_S0030400X23060097 crossref_primary_10_3390_molecules28114563 crossref_primary_10_1039_D0CP05727D crossref_primary_10_1021_acs_jpca_2c06460 crossref_primary_10_1063_1_5079626 crossref_primary_10_1063_1_5037113 crossref_primary_10_1039_D1CP04279C crossref_primary_10_1039_D3CP01313H crossref_primary_10_1016_j_jms_2022_111721 crossref_primary_10_1088_1742_6596_1290_1_012013 crossref_primary_10_1021_acs_chemrev_9b00007 crossref_primary_10_1016_j_jqsrt_2019_106656 crossref_primary_10_1063_5_0089097 crossref_primary_10_1080_00268976_2020_1837404 |
ContentType | Journal Article |
DBID | NPM |
DOI | 10.1063/1.5020295 |
DatabaseName | PubMed |
DatabaseTitle | PubMed |
DatabaseTitleList | PubMed |
Database_xml | – sequence: 1 dbid: NPM name: PubMed url: https://proxy.k.utb.cz/login?url=http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed sourceTypes: Index Database |
DeliveryMethod | no_fulltext_linktorsrc |
Discipline | Chemistry Physics |
EISSN | 1089-7690 |
ExternalDocumentID | 29495771 |
Genre | Journal Article |
GroupedDBID | --- -DZ -ET -~X 123 1UP 2-P 29K 4.4 53G 5VS 85S AAAAW AABDS AAEUA AAPUP AAYIH ABPPZ ABZEH ACBRY ACLYJ ACNCT ACZLF ADCTM AEJMO AENEX AFATG AFHCQ AGKCL AGLKD AGMXG AGTJO AHSDT AJJCW AJQPL ALEPV ALMA_UNASSIGNED_HOLDINGS AQWKA ATXIE AWQPM BDMKI BPZLN CS3 D-I DU5 EBS EJD ESX F5P FDOHQ FFFMQ HAM M6X M71 M73 N9A NPM NPSNA O-B P2P RIP RNS RQS TN5 TWZ UPT WH7 YQT YZZ ~02 |
ID | FETCH-LOGICAL-c355t-878421c79a37fb93b6c39e42538ade6e47429c33f04e52a11f95bed976f82bd42 |
IngestDate | Sat Sep 28 08:46:38 EDT 2024 |
IsDoiOpenAccess | false |
IsOpenAccess | true |
IsPeerReviewed | true |
IsScholarly | true |
Issue | 8 |
Language | English |
LinkModel | OpenURL |
MergedId | FETCHMERGED-LOGICAL-c355t-878421c79a37fb93b6c39e42538ade6e47429c33f04e52a11f95bed976f82bd42 |
ORCID | 0000000328641910 0000000316543336 000000032562500X 0000000276234992 |
OpenAccessLink | https://ir.canterbury.ac.nz/bitstream/10092/105240/2/DIHALO_Article_2017-12-21_FINAL.pdf |
PMID | 29495771 |
ParticipantIDs | pubmed_primary_29495771 |
PublicationCentury | 2000 |
PublicationDate | 2018-Feb-28 |
PublicationDateYYYYMMDD | 2018-02-28 |
PublicationDate_xml | – month: 02 year: 2018 text: 2018-Feb-28 day: 28 |
PublicationDecade | 2010 |
PublicationPlace | United States |
PublicationPlace_xml | – name: United States |
PublicationTitle | The Journal of chemical physics |
PublicationTitleAlternate | J Chem Phys |
PublicationYear | 2018 |
SSID | ssj0001724 |
Score | 2.400509 |
Snippet | Three dihalogenated methane derivatives (CH
F
, CH
FCl, and CH
Cl
) were used as model systems to compare and assess the accuracy of two different approaches... |
SourceID | pubmed |
SourceType | Index Database |
StartPage | 084102 |
Title | Comparing the accuracy of perturbative and variational calculations for predicting fundamental vibrational frequencies of dihalomethanes |
URI | https://www.ncbi.nlm.nih.gov/pubmed/29495771 |
Volume | 148 |
hasFullText | |
inHoldings | 1 |
isFullTextHit | |
isPrint | |
link | http://utb.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV3LbtQwFLWmIAQbBOX9khdsU2LHie0lGoEqFhWCVuqush2bGR7JKM2MBF_AV_FtXMdOYspDwCaKcifRKOfEPr6-D4SeOkaUqgnNZClp5qu_ZJoLDd-VyCtpiMrdEOV7VB2esFen5eli8S2JWtr2-sB8-WVeyf-gCtcAV58l-w_ITg-FC3AO-MIREIbjX2G8DE0EY8KTMmbb-e7tPojZdjCX6FDV2_vGd_C70e8HsJjtGAPnwww3nd-uGQKgnc8MiQX_d34pHe9xXYi5XocitfV6pT62vv20amIU4vuZd4nKNWNBguBCmbeOOnXetOcrsH9od4MP1ueBfp6Dbt-a1baPXbXftH6rYdKty06t38VdJ2-YPb1rrewu5iCpPnVpEJGkiNswDOdCZrwKjUSncZqJhJAiGXVzwciQt_3zhAAKzPsmDkqQxTS080yIsfk0MINKWCby0Armz9YLtblH0x7a48KPr0feVxR1AEhDNtayqopn03_w9afjfRfWMoOmOb6BrkeY8PPArJtoYZt9dHU59gDcR1deB9Ruoa8T1zBwDY9cw63DKdcwcA0nXMMp1zBwDc9cwwnXcMI1nHDNP_9Hrt1GJy9fHC8Ps9jFIzOgZXuYbgWjxHCpCu60LHRlCmlhqiiEqm1lGQdJZIrC5cyWVBHiZKltDTLZCaprRu-gS03b2HsI1y53RAidK14yzbTm1PDa0UooqYmp7qO74XWebUKplrPxRT_4reUhujZT8BG67GBssI9BaPb6yYDnd9P0hx0 |
link.rule.ids | 786 |
linkProvider | National Library of Medicine |
openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Comparing+the+accuracy+of+perturbative+and+variational+calculations+for+predicting+fundamental+vibrational+frequencies+of+dihalomethanes&rft.jtitle=The+Journal+of+chemical+physics&rft.au=Krasnoshchekov%2C+Sergey+V&rft.au=Schutski%2C+Roman+S&rft.au=Craig%2C+Norman+C&rft.au=Sibaev%2C+Marat&rft.date=2018-02-28&rft.eissn=1089-7690&rft.volume=148&rft.issue=8&rft.spage=084102&rft_id=info:doi/10.1063%2F1.5020295&rft_id=info%3Apmid%2F29495771&rft_id=info%3Apmid%2F29495771&rft.externalDocID=29495771 |