Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation

The spectroscopic and dynamic aspects of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation are investigated within an ab initio based vibronic-coupling model approach. Multireference second-order perturbation theory (CASPT2) has been employed to obtain the potential energies of t...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:The Journal of chemical physics 2003-04, Vol.118 (13), p.5880-5893
Hauptverfasser: Woywod, Clemens, Scharfe, Sandra, Krawczyk, Robert, Domcke, Wolfgang, Köppel, Horst
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 5893
container_issue 13
container_start_page 5880
container_title The Journal of chemical physics
container_volume 118
creator Woywod, Clemens
Scharfe, Sandra
Krawczyk, Robert
Domcke, Wolfgang
Köppel, Horst
description The spectroscopic and dynamic aspects of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation are investigated within an ab initio based vibronic-coupling model approach. Multireference second-order perturbation theory (CASPT2) has been employed to obtain the potential energies of the ground state and the first excited state of NH3+ as a function of symmetry-coordinate displacements. Vibronic-coupling parameters determining the Franck–Condon, Jahn–Teller, and pseudo-Jahn–Teller activity of the normal modes have been obtained from the ab initio data. The vibronic structures of the X̃ 2A1 and Ã 2E photoelectron bands of ammonia have been calculated by numerical diagonalization of the vibronic Hamiltonian matrix. All six vibrational degrees of freedom are taken into account. The effects of Jahn–Teller and pseudo-Jahn–Teller interactions on the band shape of the Ã 2E photoelectron band are analyzed. The calculation of the time-dependent population probability of the Ã 2E state reveals a radiationless decay process on a time scale of 30 fs caused by a conical intersection of the X̃ and à potential-energy surfaces, which arises from the combined effect of the Jahn–Teller splitting of the Ã 2E state and the X̃–à pseudo-Jahn–Teller interaction. In the X̃ 2A1 band, the X̃–à pseudo-Jahn–Teller coupling results in the weak excitation of a single quantum of the degenerate bending mode. This theoretical result corroborates the earlier assignment of the vibronic structure of the X̃ 2A1 photoelectron band of NH3 by Edvardsson et al. [J. Phys. B 32, 2583 (1999)].
doi_str_mv 10.1063/1.1557191
format Article
fullrecord <record><control><sourceid>crossref</sourceid><recordid>TN_cdi_crossref_primary_10_1063_1_1557191</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1063_1_1557191</sourcerecordid><originalsourceid>FETCH-LOGICAL-c227t-18c6e34efee20fc0c19158e398ce8b3b2445f385f97cc747d4bacc7911e3f8953</originalsourceid><addsrcrecordid>eNpVUL1OwzAYtBBIlMLAG3hlSPm-OIntEVVAQZVYwhw5zmdilJ_KDkhsvANvyJOQQhemu9PpTrpj7BJhhVCIa1xhnkvUeMQWCEonstBwzBYAKSa6gOKUncX4CgAo02zBXNnSGGjy1nTcD-8UJ_9iJj8OfHT80bTD9-dXSV1HgZuh4btIb82Y_Df8MFEwdp-Ks-BTS9z0_Th4w-1v2Tk7caaLdHHAJXu-uy3Xm2T7dP-wvtkmNk3llKCyBYmMHFEKzoKdh-SKhFaWVC3qNMtyJ1TutLRWZrLJajMTjUjCKZ2LJbv667VhjDGQq3bB9yZ8VAjV_qAKq8NB4gdFnFuV</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation</title><source>AIP Journals Complete</source><source>AIP Digital Archive</source><creator>Woywod, Clemens ; Scharfe, Sandra ; Krawczyk, Robert ; Domcke, Wolfgang ; Köppel, Horst</creator><creatorcontrib>Woywod, Clemens ; Scharfe, Sandra ; Krawczyk, Robert ; Domcke, Wolfgang ; Köppel, Horst</creatorcontrib><description>The spectroscopic and dynamic aspects of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation are investigated within an ab initio based vibronic-coupling model approach. Multireference second-order perturbation theory (CASPT2) has been employed to obtain the potential energies of the ground state and the first excited state of NH3+ as a function of symmetry-coordinate displacements. Vibronic-coupling parameters determining the Franck–Condon, Jahn–Teller, and pseudo-Jahn–Teller activity of the normal modes have been obtained from the ab initio data. The vibronic structures of the X̃ 2A1 and Ã 2E photoelectron bands of ammonia have been calculated by numerical diagonalization of the vibronic Hamiltonian matrix. All six vibrational degrees of freedom are taken into account. The effects of Jahn–Teller and pseudo-Jahn–Teller interactions on the band shape of the Ã 2E photoelectron band are analyzed. The calculation of the time-dependent population probability of the Ã 2E state reveals a radiationless decay process on a time scale of 30 fs caused by a conical intersection of the X̃ and à potential-energy surfaces, which arises from the combined effect of the Jahn–Teller splitting of the Ã 2E state and the X̃–à pseudo-Jahn–Teller interaction. In the X̃ 2A1 band, the X̃–à pseudo-Jahn–Teller coupling results in the weak excitation of a single quantum of the degenerate bending mode. This theoretical result corroborates the earlier assignment of the vibronic structure of the X̃ 2A1 photoelectron band of NH3 by Edvardsson et al. [J. Phys. B 32, 2583 (1999)].</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.1557191</identifier><language>eng</language><ispartof>The Journal of chemical physics, 2003-04, Vol.118 (13), p.5880-5893</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c227t-18c6e34efee20fc0c19158e398ce8b3b2445f385f97cc747d4bacc7911e3f8953</citedby><cites>FETCH-LOGICAL-c227t-18c6e34efee20fc0c19158e398ce8b3b2445f385f97cc747d4bacc7911e3f8953</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Woywod, Clemens</creatorcontrib><creatorcontrib>Scharfe, Sandra</creatorcontrib><creatorcontrib>Krawczyk, Robert</creatorcontrib><creatorcontrib>Domcke, Wolfgang</creatorcontrib><creatorcontrib>Köppel, Horst</creatorcontrib><title>Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation</title><title>The Journal of chemical physics</title><description>The spectroscopic and dynamic aspects of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation are investigated within an ab initio based vibronic-coupling model approach. Multireference second-order perturbation theory (CASPT2) has been employed to obtain the potential energies of the ground state and the first excited state of NH3+ as a function of symmetry-coordinate displacements. Vibronic-coupling parameters determining the Franck–Condon, Jahn–Teller, and pseudo-Jahn–Teller activity of the normal modes have been obtained from the ab initio data. The vibronic structures of the X̃ 2A1 and Ã 2E photoelectron bands of ammonia have been calculated by numerical diagonalization of the vibronic Hamiltonian matrix. All six vibrational degrees of freedom are taken into account. The effects of Jahn–Teller and pseudo-Jahn–Teller interactions on the band shape of the Ã 2E photoelectron band are analyzed. The calculation of the time-dependent population probability of the Ã 2E state reveals a radiationless decay process on a time scale of 30 fs caused by a conical intersection of the X̃ and à potential-energy surfaces, which arises from the combined effect of the Jahn–Teller splitting of the Ã 2E state and the X̃–à pseudo-Jahn–Teller interaction. In the X̃ 2A1 band, the X̃–à pseudo-Jahn–Teller coupling results in the weak excitation of a single quantum of the degenerate bending mode. This theoretical result corroborates the earlier assignment of the vibronic structure of the X̃ 2A1 photoelectron band of NH3 by Edvardsson et al. [J. Phys. B 32, 2583 (1999)].</description><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNpVUL1OwzAYtBBIlMLAG3hlSPm-OIntEVVAQZVYwhw5zmdilJ_KDkhsvANvyJOQQhemu9PpTrpj7BJhhVCIa1xhnkvUeMQWCEonstBwzBYAKSa6gOKUncX4CgAo02zBXNnSGGjy1nTcD-8UJ_9iJj8OfHT80bTD9-dXSV1HgZuh4btIb82Y_Df8MFEwdp-Ks-BTS9z0_Th4w-1v2Tk7caaLdHHAJXu-uy3Xm2T7dP-wvtkmNk3llKCyBYmMHFEKzoKdh-SKhFaWVC3qNMtyJ1TutLRWZrLJajMTjUjCKZ2LJbv667VhjDGQq3bB9yZ8VAjV_qAKq8NB4gdFnFuV</recordid><startdate>20030401</startdate><enddate>20030401</enddate><creator>Woywod, Clemens</creator><creator>Scharfe, Sandra</creator><creator>Krawczyk, Robert</creator><creator>Domcke, Wolfgang</creator><creator>Köppel, Horst</creator><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20030401</creationdate><title>Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation</title><author>Woywod, Clemens ; Scharfe, Sandra ; Krawczyk, Robert ; Domcke, Wolfgang ; Köppel, Horst</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c227t-18c6e34efee20fc0c19158e398ce8b3b2445f385f97cc747d4bacc7911e3f8953</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Woywod, Clemens</creatorcontrib><creatorcontrib>Scharfe, Sandra</creatorcontrib><creatorcontrib>Krawczyk, Robert</creatorcontrib><creatorcontrib>Domcke, Wolfgang</creatorcontrib><creatorcontrib>Köppel, Horst</creatorcontrib><collection>CrossRef</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Woywod, Clemens</au><au>Scharfe, Sandra</au><au>Krawczyk, Robert</au><au>Domcke, Wolfgang</au><au>Köppel, Horst</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation</atitle><jtitle>The Journal of chemical physics</jtitle><date>2003-04-01</date><risdate>2003</risdate><volume>118</volume><issue>13</issue><spage>5880</spage><epage>5893</epage><pages>5880-5893</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><abstract>The spectroscopic and dynamic aspects of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation are investigated within an ab initio based vibronic-coupling model approach. Multireference second-order perturbation theory (CASPT2) has been employed to obtain the potential energies of the ground state and the first excited state of NH3+ as a function of symmetry-coordinate displacements. Vibronic-coupling parameters determining the Franck–Condon, Jahn–Teller, and pseudo-Jahn–Teller activity of the normal modes have been obtained from the ab initio data. The vibronic structures of the X̃ 2A1 and Ã 2E photoelectron bands of ammonia have been calculated by numerical diagonalization of the vibronic Hamiltonian matrix. All six vibrational degrees of freedom are taken into account. The effects of Jahn–Teller and pseudo-Jahn–Teller interactions on the band shape of the Ã 2E photoelectron band are analyzed. The calculation of the time-dependent population probability of the Ã 2E state reveals a radiationless decay process on a time scale of 30 fs caused by a conical intersection of the X̃ and à potential-energy surfaces, which arises from the combined effect of the Jahn–Teller splitting of the Ã 2E state and the X̃–à pseudo-Jahn–Teller interaction. In the X̃ 2A1 band, the X̃–à pseudo-Jahn–Teller coupling results in the weak excitation of a single quantum of the degenerate bending mode. This theoretical result corroborates the earlier assignment of the vibronic structure of the X̃ 2A1 photoelectron band of NH3 by Edvardsson et al. [J. Phys. B 32, 2583 (1999)].</abstract><doi>10.1063/1.1557191</doi><tpages>14</tpages></addata></record>
fulltext fulltext
identifier ISSN: 0021-9606
ispartof The Journal of chemical physics, 2003-04, Vol.118 (13), p.5880-5893
issn 0021-9606
1089-7690
language eng
recordid cdi_crossref_primary_10_1063_1_1557191
source AIP Journals Complete; AIP Digital Archive
title Theoretical investigation of Jahn–Teller and pseudo-Jahn–Teller interactions in the ammonia cation
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-04T18%3A03%3A34IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-crossref&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Theoretical%20investigation%20of%20Jahn%E2%80%93Teller%20and%20pseudo-Jahn%E2%80%93Teller%20interactions%20in%20the%20ammonia%20cation&rft.jtitle=The%20Journal%20of%20chemical%20physics&rft.au=Woywod,%20Clemens&rft.date=2003-04-01&rft.volume=118&rft.issue=13&rft.spage=5880&rft.epage=5893&rft.pages=5880-5893&rft.issn=0021-9606&rft.eissn=1089-7690&rft_id=info:doi/10.1063/1.1557191&rft_dat=%3Ccrossref%3E10_1063_1_1557191%3C/crossref%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true