Ab Initio and Density Functional Theoretical Studies of Structures, Vibrational Spectra, and Dimerization Dynamics of Simple Transient Germenes

Structures and harmonic vibrational frequencies for several simple transient germenes, H2GeCH2 (1), MeHGeCH2 (2), Me2GeCH2 (3), FHGeCH2 (4), and H2GeCHF (5), and their dimerization and transition state energies for the head-to-tail and head-to-head self-coupling have been calculated by ab initi...

Full description

Saved in:
Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 1998-01, Vol.102 (4), p.744-753
Main Authors: Kudin, Konstantin N, Margrave, John L, Khabashesku, Valery N
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
cited_by cdi_FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3
cites cdi_FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3
container_end_page 753
container_issue 4
container_start_page 744
container_title The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory
container_volume 102
creator Kudin, Konstantin N
Margrave, John L
Khabashesku, Valery N
description Structures and harmonic vibrational frequencies for several simple transient germenes, H2GeCH2 (1), MeHGeCH2 (2), Me2GeCH2 (3), FHGeCH2 (4), and H2GeCHF (5), and their dimerization and transition state energies for the head-to-tail and head-to-head self-coupling have been calculated by ab initio HF 3-21G and 6-311G(d,p) and density functional theory B3LYP/6-311G(d,p) methods. The effect of substituents on the GeC bond lengths and bond orders, as well as frequencies and force constants of the GeC stretch, is predicted to be relatively small in germenes 1 − 3 and be substantially stronger in the F-substituted molecules 4 and 5. Within the limits of the HF/3-21G method, the head-to-tail cyclodimerizations of all studied germenes 1 − 5 were found to be more exothermic than the head-to-head processes and to proceed with very low or zero barriers. This conclusion is confirmed for 1 − 4 by the higher level calculations with the 6-311G(d,p) basis set at HF and B3LYP levels, which in the case of 5 leads to the opposite result such as a substantial barrier for the head-to-tail dimerization and a lesser exothermicity of this process relative to the head-to-head one. The comparison of the HF/3-21G data available for the whole series of similarly substituted silenes with those calculated for 1 − 5 at the same level of theory indicate somewhat easier dimerization of germenes with respect to their double-bonded silicon analogues.
doi_str_mv 10.1021/jp972006p
format article
fullrecord <record><control><sourceid>acs_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_jp972006p</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>c606581600</sourcerecordid><originalsourceid>FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3</originalsourceid><addsrcrecordid>eNptkM1OwzAQhCMEElA48Aa-cEBqwHbiJD4ioOWnEoiWHrhYjrMRLo0T2Y5EeQleGUMqTpx2NPvtrDRRdELwOcGUXKw6nlOMs24nOiCM4phRwnaDxgWPWZbw_ejQuRXGmCQ0PYi-Lkt0Z7TXLZKmQtdgnPYbNOmNCp6Ra7R4g9aC1yroue8rDQ61dZC2V7634MZoqUsrt_i8A-WtHA9xugGrP3936HpjZKPVcK2bbg1oYWX4B8ajKdgGDLijaK-WawfH2zmKXiY3i6vbePY4vbu6nMWScubjlJVUQQkJ5zhPOWd1MIqU8CKnUDHMSZ1VIAtQBVWyAs5TVdZFmhcZUxUrk1F0NuQq2zpnoRad1Y20G0Gw-GlS_DUZ2HhgtfPw8QdK-y6yPMmZWDzNBZvcvz4ss4l4DvzpwEvlxKrtbejF_ZP7DfSshKM</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Ab Initio and Density Functional Theoretical Studies of Structures, Vibrational Spectra, and Dimerization Dynamics of Simple Transient Germenes</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read &amp; Publish Agreement 2022-2024 (Reading list)</source><creator>Kudin, Konstantin N ; Margrave, John L ; Khabashesku, Valery N</creator><creatorcontrib>Kudin, Konstantin N ; Margrave, John L ; Khabashesku, Valery N</creatorcontrib><description>Structures and harmonic vibrational frequencies for several simple transient germenes, H2GeCH2 (1), MeHGeCH2 (2), Me2GeCH2 (3), FHGeCH2 (4), and H2GeCHF (5), and their dimerization and transition state energies for the head-to-tail and head-to-head self-coupling have been calculated by ab initio HF 3-21G and 6-311G(d,p) and density functional theory B3LYP/6-311G(d,p) methods. The effect of substituents on the GeC bond lengths and bond orders, as well as frequencies and force constants of the GeC stretch, is predicted to be relatively small in germenes 1 − 3 and be substantially stronger in the F-substituted molecules 4 and 5. Within the limits of the HF/3-21G method, the head-to-tail cyclodimerizations of all studied germenes 1 − 5 were found to be more exothermic than the head-to-head processes and to proceed with very low or zero barriers. This conclusion is confirmed for 1 − 4 by the higher level calculations with the 6-311G(d,p) basis set at HF and B3LYP levels, which in the case of 5 leads to the opposite result such as a substantial barrier for the head-to-tail dimerization and a lesser exothermicity of this process relative to the head-to-head one. The comparison of the HF/3-21G data available for the whole series of similarly substituted silenes with those calculated for 1 − 5 at the same level of theory indicate somewhat easier dimerization of germenes with respect to their double-bonded silicon analogues.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp972006p</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory, 1998-01, Vol.102 (4), p.744-753</ispartof><rights>Copyright © 1998 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3</citedby><cites>FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids></links><search><creatorcontrib>Kudin, Konstantin N</creatorcontrib><creatorcontrib>Margrave, John L</creatorcontrib><creatorcontrib>Khabashesku, Valery N</creatorcontrib><title>Ab Initio and Density Functional Theoretical Studies of Structures, Vibrational Spectra, and Dimerization Dynamics of Simple Transient Germenes</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>Structures and harmonic vibrational frequencies for several simple transient germenes, H2GeCH2 (1), MeHGeCH2 (2), Me2GeCH2 (3), FHGeCH2 (4), and H2GeCHF (5), and their dimerization and transition state energies for the head-to-tail and head-to-head self-coupling have been calculated by ab initio HF 3-21G and 6-311G(d,p) and density functional theory B3LYP/6-311G(d,p) methods. The effect of substituents on the GeC bond lengths and bond orders, as well as frequencies and force constants of the GeC stretch, is predicted to be relatively small in germenes 1 − 3 and be substantially stronger in the F-substituted molecules 4 and 5. Within the limits of the HF/3-21G method, the head-to-tail cyclodimerizations of all studied germenes 1 − 5 were found to be more exothermic than the head-to-head processes and to proceed with very low or zero barriers. This conclusion is confirmed for 1 − 4 by the higher level calculations with the 6-311G(d,p) basis set at HF and B3LYP levels, which in the case of 5 leads to the opposite result such as a substantial barrier for the head-to-tail dimerization and a lesser exothermicity of this process relative to the head-to-head one. The comparison of the HF/3-21G data available for the whole series of similarly substituted silenes with those calculated for 1 − 5 at the same level of theory indicate somewhat easier dimerization of germenes with respect to their double-bonded silicon analogues.</description><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1998</creationdate><recordtype>article</recordtype><recordid>eNptkM1OwzAQhCMEElA48Aa-cEBqwHbiJD4ioOWnEoiWHrhYjrMRLo0T2Y5EeQleGUMqTpx2NPvtrDRRdELwOcGUXKw6nlOMs24nOiCM4phRwnaDxgWPWZbw_ejQuRXGmCQ0PYi-Lkt0Z7TXLZKmQtdgnPYbNOmNCp6Ra7R4g9aC1yroue8rDQ61dZC2V7634MZoqUsrt_i8A-WtHA9xugGrP3936HpjZKPVcK2bbg1oYWX4B8ajKdgGDLijaK-WawfH2zmKXiY3i6vbePY4vbu6nMWScubjlJVUQQkJ5zhPOWd1MIqU8CKnUDHMSZ1VIAtQBVWyAs5TVdZFmhcZUxUrk1F0NuQq2zpnoRad1Y20G0Gw-GlS_DUZ2HhgtfPw8QdK-y6yPMmZWDzNBZvcvz4ss4l4DvzpwEvlxKrtbejF_ZP7DfSshKM</recordid><startdate>19980122</startdate><enddate>19980122</enddate><creator>Kudin, Konstantin N</creator><creator>Margrave, John L</creator><creator>Khabashesku, Valery N</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19980122</creationdate><title>Ab Initio and Density Functional Theoretical Studies of Structures, Vibrational Spectra, and Dimerization Dynamics of Simple Transient Germenes</title><author>Kudin, Konstantin N ; Margrave, John L ; Khabashesku, Valery N</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1998</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kudin, Konstantin N</creatorcontrib><creatorcontrib>Margrave, John L</creatorcontrib><creatorcontrib>Khabashesku, Valery N</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kudin, Konstantin N</au><au>Margrave, John L</au><au>Khabashesku, Valery N</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Ab Initio and Density Functional Theoretical Studies of Structures, Vibrational Spectra, and Dimerization Dynamics of Simple Transient Germenes</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, &amp; general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>1998-01-22</date><risdate>1998</risdate><volume>102</volume><issue>4</issue><spage>744</spage><epage>753</epage><pages>744-753</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><notes>ark:/67375/TPS-5FJZKV6F-R</notes><notes>Dedicated to the 65th birthday of Professor Oleg M. Nefedov, Member and Vice-President of the Russian Academy of Sciences, and one of the major contributors to the chemistry of group 14 transient molecules.</notes><notes>istex:197C0941F286CE222BB2D2179AF4B346E50BDD22</notes><abstract>Structures and harmonic vibrational frequencies for several simple transient germenes, H2GeCH2 (1), MeHGeCH2 (2), Me2GeCH2 (3), FHGeCH2 (4), and H2GeCHF (5), and their dimerization and transition state energies for the head-to-tail and head-to-head self-coupling have been calculated by ab initio HF 3-21G and 6-311G(d,p) and density functional theory B3LYP/6-311G(d,p) methods. The effect of substituents on the GeC bond lengths and bond orders, as well as frequencies and force constants of the GeC stretch, is predicted to be relatively small in germenes 1 − 3 and be substantially stronger in the F-substituted molecules 4 and 5. Within the limits of the HF/3-21G method, the head-to-tail cyclodimerizations of all studied germenes 1 − 5 were found to be more exothermic than the head-to-head processes and to proceed with very low or zero barriers. This conclusion is confirmed for 1 − 4 by the higher level calculations with the 6-311G(d,p) basis set at HF and B3LYP levels, which in the case of 5 leads to the opposite result such as a substantial barrier for the head-to-tail dimerization and a lesser exothermicity of this process relative to the head-to-head one. The comparison of the HF/3-21G data available for the whole series of similarly substituted silenes with those calculated for 1 − 5 at the same level of theory indicate somewhat easier dimerization of germenes with respect to their double-bonded silicon analogues.</abstract><pub>American Chemical Society</pub><doi>10.1021/jp972006p</doi><tpages>10</tpages></addata></record>
fulltext fulltext
identifier ISSN: 1089-5639
ispartof The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 1998-01, Vol.102 (4), p.744-753
issn 1089-5639
1520-5215
language eng
recordid cdi_crossref_primary_10_1021_jp972006p
source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
title Ab Initio and Density Functional Theoretical Studies of Structures, Vibrational Spectra, and Dimerization Dynamics of Simple Transient Germenes
url http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-09-22T04%3A30%3A29IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Ab%20Initio%20and%20Density%20Functional%20Theoretical%20Studies%20of%20Structures,%20Vibrational%20Spectra,%20and%20Dimerization%20Dynamics%20of%20Simple%20Transient%20Germenes&rft.jtitle=The%20journal%20of%20physical%20chemistry.%20A,%20Molecules,%20spectroscopy,%20kinetics,%20environment,%20&%20general%20theory&rft.au=Kudin,%20Konstantin%20N&rft.date=1998-01-22&rft.volume=102&rft.issue=4&rft.spage=744&rft.epage=753&rft.pages=744-753&rft.issn=1089-5639&rft.eissn=1520-5215&rft_id=info:doi/10.1021/jp972006p&rft_dat=%3Cacs_cross%3Ec606581600%3C/acs_cross%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a295t-45b2cebe399074995f5b28419872ed5091f6dea8ec82cade994cbf847865cd5b3%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true