Vibrational analysis of methyl cation-Rare gas atom complexes: CH3 +-Rg (Rg = He, Ne, Ar, Kr)
The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with...
Saved in:
| Published in: | The Journal of chemical physics Vol. 150; no. 8; p. 084306 |
|---|---|
| Main Authors: | , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
28.02.2019
|
| ISSN: | 1089-7690, 1089-7690 |
| Online Access: | Get more information |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Abstract | The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH3 +-He has been investigated on the basis of semiclassical instanton theory. These calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H3O+, suggest that tunneling effects for vibrationally excited states should be very small.The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH3 +-He has been investigated on the basis of semiclassical instanton theory. These calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H3O+, suggest that tunneling effects for vibrationally excited states should be very small. |
|---|---|
| AbstractList | The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH3 +-He has been investigated on the basis of semiclassical instanton theory. These calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H3O+, suggest that tunneling effects for vibrationally excited states should be very small.The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH3 +-He has been investigated on the basis of semiclassical instanton theory. These calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H3O+, suggest that tunneling effects for vibrationally excited states should be very small. |
| Author | Hallmen, Philipp P Kästner, Johannes Meisner, Jan Rauhut, Guntram |
| Author_xml | – sequence: 1 givenname: Jan surname: Meisner fullname: Meisner, Jan – sequence: 2 givenname: Philipp P surname: Hallmen fullname: Hallmen, Philipp P – sequence: 3 givenname: Johannes surname: Kästner fullname: Kästner, Johannes – sequence: 4 givenname: Guntram surname: Rauhut fullname: Rauhut, Guntram |
| BookMark | eNpNjF1LwzAYhYNMcJte-A_ey4nrfJMmbSp4MYo6cSgM9U5GmqSzkjaz6cD9e-vHhRfnnIdz4IzIoPGNJeSU4oxiEl_QmUDJKeIBGVKUWZQmGQ7-8REZhfCOiDRlfEheX6qiVV3lG-VA9bYPVQBfQm27t70D_bNFK9Va2KgAqvM1aF9vnf204RLyRQzn0WoDk15XsLBTeOg1b6dw354dk8NSuWBP_nJMnm-un_JFtHy8vcvny0gzgV1ES0rjMsNCWm0LTrNYZJyajIm-YUZrqaU0DI0RWsUs0Vrzb5YGRaI4Z2My-f3dtv5jZ0O3rqugrXOqsX4X1ozKVDDOMGVfMhZUqg |
| ContentType | Journal Article |
| DBID | 7X8 |
| DOI | 10.1063/1.5084100 |
| DatabaseName | MEDLINE - Academic |
| DatabaseTitle | MEDLINE - Academic |
| DatabaseTitleList | MEDLINE - Academic |
| Database_xml | – sequence: 1 dbid: 7X8 name: MEDLINE - Academic url: https://search.proquest.com/medline sourceTypes: Aggregation Database |
| DeliveryMethod | no_fulltext_linktorsrc |
| Discipline | Chemistry Physics |
| EISSN | 1089-7690 |
| GroupedDBID | --- -DZ -ET -~X 123 1UP 2-P 29K 4.4 53G 5VS 7X8 85S AAAAW AABDS AAGWI AAPUP AAYIH ABJGX ABPPZ ABZEH ACBRY ACLYJ ACNCT ACZLF ADCTM ADMLS 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 F5P FDOHQ FFFMQ HAM M6X M71 M73 N9A NPSNA O-B P2P RIP RNS RQS TN5 TWZ UPT WH7 YQT YZZ ~02 |
| ID | FETCH-LOGICAL-c250t-1f113f90b8eceb41935941d925b8e2dcc8c88d20dd5ca326ccc4dd5c8d056a442 |
| IEDL.DBID | 7X8 |
| ISICitedReferencesCount | 19 |
| ISICitedReferencesURI | http://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestLinkType=CitingArticles&DestApp=WOS_CPL&KeyUT=000460034700021&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| ISSN | 1089-7690 |
| IngestDate | Thu Jul 10 23:31:47 EDT 2025 |
| IsPeerReviewed | true |
| IsScholarly | true |
| Issue | 8 |
| Language | English |
| LinkModel | DirectLink |
| MergedId | FETCHMERGED-LOGICAL-c250t-1f113f90b8eceb41935941d925b8e2dcc8c88d20dd5ca326ccc4dd5c8d056a442 |
| Notes | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| PQID | 2187524207 |
| PQPubID | 23479 |
| ParticipantIDs | proquest_miscellaneous_2187524207 |
| PublicationCentury | 2000 |
| PublicationDate | 20190228 |
| PublicationDateYYYYMMDD | 2019-02-28 |
| PublicationDate_xml | – month: 02 year: 2019 text: 20190228 day: 28 |
| PublicationDecade | 2010 |
| PublicationTitle | The Journal of chemical physics |
| PublicationYear | 2019 |
| SSID | ssj0001724 |
| Score | 2.3910356 |
| Snippet | The vibrational spectra of simple CH3 +-Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on... |
| SourceID | proquest |
| SourceType | Aggregation Database |
| StartPage | 084306 |
| Title | Vibrational analysis of methyl cation-Rare gas atom complexes: CH3 +-Rg (Rg = He, Ne, Ar, Kr) |
| URI | https://www.proquest.com/docview/2187524207 |
| Volume | 150 |
| WOSCitedRecordID | wos000460034700021&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| hasFullText | |
| inHoldings | 1 |
| isFullTextHit | |
| isPrint | |
| link | http://cvtisr.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwpV3fS8MwEA7qFH3xx1T8TQQfFBfXtOnaCCJjOAbCkKGyFxnpJRmCdrpO0f_eS9uxB18EC4FS-tDm2rvvLl_uI-QkhIYHDWWZRQMzYY1FPxhaNIjVmOPaKLYqF5uIut2435d3ZcEtK2mVU5-YO2o9Alcjr2MoikKMJ150_fbOnGqUW10tJTTmSSVAKOMoXVF_1i0cg7MoCPaSRZgGTjsLNYI6v0BkIrjn_fLBeWBpr_33kdbJagkpabP4BjbInEmrZLk1VXKrkqWc5gnZJnl6dNlxUf6jquxHQkeWOiHp7xda1O9YT40NHaqMYkb-SnPWufky2SVtdQJ6znpDeorjinZMjXZxNMc1ejs-2yIP7Zv7VoeVAgsMEPlMGLecB1Z6SWzAJIK7XbqCa-mHeMXXADHEsfY9rUNQiPMAQLjzWCNsUkL422QhHaVmh9DANpQ0wgPpg5A8SPCwMrEGIm2l8nfJ8XQOB_j2blVCpWb0kQ1ms7j3h3v2yQpCFllsKj8gFYs_qTkki_A5ec7GR7n9fwDurLiO |
| linkProvider | ProQuest |
| 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=Vibrational+analysis+of+methyl+cation-Rare+gas+atom+complexes%3A+CH3+%2B-Rg+%28Rg+%3D+He%2C+Ne%2C+Ar%2C+Kr%29&rft.jtitle=The+Journal+of+chemical+physics&rft.au=Meisner%2C+Jan&rft.au=Hallmen%2C+Philipp+P&rft.au=K%C3%A4stner%2C+Johannes&rft.au=Rauhut%2C+Guntram&rft.date=2019-02-28&rft.issn=1089-7690&rft.eissn=1089-7690&rft.volume=150&rft.issue=8&rft.spage=084306&rft_id=info:doi/10.1063%2F1.5084100&rft.externalDBID=NO_FULL_TEXT |
| thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=1089-7690&client=summon |
| thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=1089-7690&client=summon |
| thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=1089-7690&client=summon |