Enthalpy of formation and anharmonic force field of diacetylene
The enthalpy of formation of diacetylene ( C 4 H 2 ) is pinpointed using state-of-the-art theoretical methods, accounting for high-order electron correlation, relativistic effects, non-Born-Oppenheimer corrections, and vibrational anharmonicity. Molecular energies are determined from coupled cluster...
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creator | Simmonett, Andrew C. Schaefer, Henry F. Allen, Wesley D. |
description | The enthalpy of formation of diacetylene
(
C
4
H
2
)
is pinpointed using state-of-the-art theoretical methods, accounting for high-order electron correlation, relativistic effects, non-Born-Oppenheimer corrections, and vibrational anharmonicity. Molecular energies are determined from coupled cluster theory with single and double excitations (CCSD), perturbative triples [CCSD(T)], full triples (CCSDT), and perturbative quadruples [CCSDT(Q)], in concert with correlation-consistent basis sets (
cc-pV
X
Z
,
X
=
D
, T, Q, 5, 6) that facilitate extrapolations to the complete basis set limit. The first full quartic force field of diacetylene is determined at the highly accurate all-electron CCSD(T) level with a cc-pCVQZ basis, which includes tight functions for core correlation. Application of second-order vibrational perturbation theory to our anharmonic force field yields fundamental frequencies with a mean absolute difference of only
3.9
cm
−
1
relative to the experimental band origins, without the use of any empirical scale factors. By a focal point approach, we converge on an enthalpy change for the isogyric reaction
2
H
-
C
≡
C
-
H
→
H
-
C
≡
C
-
C
≡
C
-
H
+
H
2
of (
+
0.03
,
+
0.81
)
kcal
mol
−
1
at (0, 298.15) K. With the precisely established
Δ
f
H
°
of acetylene, we thus obtain
Δ
f
H
°
(
C
4
H
2
)
=
(
109.4
,
109.7
)
±
0.3
kcal
mol
−
1
at (0, 298.15) K. Previous estimates of the diacetylene enthalpy of formation range from 102 to
120
kcal
mol
−
1
. |
doi_str_mv | 10.1063/1.3054917 |
format | Article |
fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_66890639</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>66890639</sourcerecordid><originalsourceid>FETCH-LOGICAL-c404t-e1a3571a21cd675a9a0fc5f375a3365576d6d43251608ab76738fb2c344025383</originalsourceid><addsrcrecordid>eNp1kE1LAzEQhoMotlYP_gHZk-Bh62SzSTYXRUr9gIIXPYc0H3Rld1OT3UP_vand4kmGYV6Yh_fwIHSNYY6BkXs8J0BLgfkJmmKoRM6ZgFM0BShwLhiwCbqI8QsAMC_KczTBIg3hYooel12_Uc12l3mXOR9a1de-y1Rn0m5UaH1X6_1D28zVtjF7ztRK237X2M5eojOnmmivxjtDn8_Lj8Vrvnp_eVs8rXJdQtnnFitCOVYF1oZxqoQCp6kjKRLCKOXMMFOSgmIGlVpzxknl1oUmZQkFJRWZodtD7zb478HGXrZ11LZpVGf9ECVjlUgqRALvDqAOPsZgndyGulVhJzHIvS2J5WgrsTdj6bBurfkjRz0JeDgAUdf9r5n_244ipXfyKJL8AEHdeA4</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>66890639</pqid></control><display><type>article</type><title>Enthalpy of formation and anharmonic force field of diacetylene</title><source>AIP Journals Complete</source><source>AIP Digital Archive</source><source>Alma/SFX Local Collection</source><creator>Simmonett, Andrew C. ; Schaefer, Henry F. ; Allen, Wesley D.</creator><creatorcontrib>Simmonett, Andrew C. ; Schaefer, Henry F. ; Allen, Wesley D.</creatorcontrib><description>The enthalpy of formation of diacetylene
(
C
4
H
2
)
is pinpointed using state-of-the-art theoretical methods, accounting for high-order electron correlation, relativistic effects, non-Born-Oppenheimer corrections, and vibrational anharmonicity. Molecular energies are determined from coupled cluster theory with single and double excitations (CCSD), perturbative triples [CCSD(T)], full triples (CCSDT), and perturbative quadruples [CCSDT(Q)], in concert with correlation-consistent basis sets (
cc-pV
X
Z
,
X
=
D
, T, Q, 5, 6) that facilitate extrapolations to the complete basis set limit. The first full quartic force field of diacetylene is determined at the highly accurate all-electron CCSD(T) level with a cc-pCVQZ basis, which includes tight functions for core correlation. Application of second-order vibrational perturbation theory to our anharmonic force field yields fundamental frequencies with a mean absolute difference of only
3.9
cm
−
1
relative to the experimental band origins, without the use of any empirical scale factors. By a focal point approach, we converge on an enthalpy change for the isogyric reaction
2
H
-
C
≡
C
-
H
→
H
-
C
≡
C
-
C
≡
C
-
H
+
H
2
of (
+
0.03
,
+
0.81
)
kcal
mol
−
1
at (0, 298.15) K. With the precisely established
Δ
f
H
°
of acetylene, we thus obtain
Δ
f
H
°
(
C
4
H
2
)
=
(
109.4
,
109.7
)
±
0.3
kcal
mol
−
1
at (0, 298.15) K. Previous estimates of the diacetylene enthalpy of formation range from 102 to
120
kcal
mol
−
1
.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.3054917</identifier><identifier>PMID: 19191379</identifier><identifier>CODEN: JCPSA6</identifier><language>eng</language><publisher>United States: American Institute of Physics</publisher><ispartof>The Journal of chemical physics, 2009-01, Vol.130 (4), p.044301-044301-10</ispartof><rights>2009 American Institute of Physics</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c404t-e1a3571a21cd675a9a0fc5f375a3365576d6d43251608ab76738fb2c344025383</citedby><cites>FETCH-LOGICAL-c404t-e1a3571a21cd675a9a0fc5f375a3365576d6d43251608ab76738fb2c344025383</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,778,782,792,1556,4500,27911,27912</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/19191379$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Simmonett, Andrew C.</creatorcontrib><creatorcontrib>Schaefer, Henry F.</creatorcontrib><creatorcontrib>Allen, Wesley D.</creatorcontrib><title>Enthalpy of formation and anharmonic force field of diacetylene</title><title>The Journal of chemical physics</title><addtitle>J Chem Phys</addtitle><description>The enthalpy of formation of diacetylene
(
C
4
H
2
)
is pinpointed using state-of-the-art theoretical methods, accounting for high-order electron correlation, relativistic effects, non-Born-Oppenheimer corrections, and vibrational anharmonicity. Molecular energies are determined from coupled cluster theory with single and double excitations (CCSD), perturbative triples [CCSD(T)], full triples (CCSDT), and perturbative quadruples [CCSDT(Q)], in concert with correlation-consistent basis sets (
cc-pV
X
Z
,
X
=
D
, T, Q, 5, 6) that facilitate extrapolations to the complete basis set limit. The first full quartic force field of diacetylene is determined at the highly accurate all-electron CCSD(T) level with a cc-pCVQZ basis, which includes tight functions for core correlation. Application of second-order vibrational perturbation theory to our anharmonic force field yields fundamental frequencies with a mean absolute difference of only
3.9
cm
−
1
relative to the experimental band origins, without the use of any empirical scale factors. By a focal point approach, we converge on an enthalpy change for the isogyric reaction
2
H
-
C
≡
C
-
H
→
H
-
C
≡
C
-
C
≡
C
-
H
+
H
2
of (
+
0.03
,
+
0.81
)
kcal
mol
−
1
at (0, 298.15) K. With the precisely established
Δ
f
H
°
of acetylene, we thus obtain
Δ
f
H
°
(
C
4
H
2
)
=
(
109.4
,
109.7
)
±
0.3
kcal
mol
−
1
at (0, 298.15) K. Previous estimates of the diacetylene enthalpy of formation range from 102 to
120
kcal
mol
−
1
.</description><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNp1kE1LAzEQhoMotlYP_gHZk-Bh62SzSTYXRUr9gIIXPYc0H3Rld1OT3UP_vand4kmGYV6Yh_fwIHSNYY6BkXs8J0BLgfkJmmKoRM6ZgFM0BShwLhiwCbqI8QsAMC_KczTBIg3hYooel12_Uc12l3mXOR9a1de-y1Rn0m5UaH1X6_1D28zVtjF7ztRK237X2M5eojOnmmivxjtDn8_Lj8Vrvnp_eVs8rXJdQtnnFitCOVYF1oZxqoQCp6kjKRLCKOXMMFOSgmIGlVpzxknl1oUmZQkFJRWZodtD7zb478HGXrZ11LZpVGf9ECVjlUgqRALvDqAOPsZgndyGulVhJzHIvS2J5WgrsTdj6bBurfkjRz0JeDgAUdf9r5n_244ipXfyKJL8AEHdeA4</recordid><startdate>20090128</startdate><enddate>20090128</enddate><creator>Simmonett, Andrew C.</creator><creator>Schaefer, Henry F.</creator><creator>Allen, Wesley D.</creator><general>American Institute of Physics</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20090128</creationdate><title>Enthalpy of formation and anharmonic force field of diacetylene</title><author>Simmonett, Andrew C. ; Schaefer, Henry F. ; Allen, Wesley D.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c404t-e1a3571a21cd675a9a0fc5f375a3365576d6d43251608ab76738fb2c344025383</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Simmonett, Andrew C.</creatorcontrib><creatorcontrib>Schaefer, Henry F.</creatorcontrib><creatorcontrib>Allen, Wesley D.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Simmonett, Andrew C.</au><au>Schaefer, Henry F.</au><au>Allen, Wesley D.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Enthalpy of formation and anharmonic force field of diacetylene</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2009-01-28</date><risdate>2009</risdate><volume>130</volume><issue>4</issue><spage>044301</spage><epage>044301-10</epage><pages>044301-044301-10</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>The enthalpy of formation of diacetylene
(
C
4
H
2
)
is pinpointed using state-of-the-art theoretical methods, accounting for high-order electron correlation, relativistic effects, non-Born-Oppenheimer corrections, and vibrational anharmonicity. Molecular energies are determined from coupled cluster theory with single and double excitations (CCSD), perturbative triples [CCSD(T)], full triples (CCSDT), and perturbative quadruples [CCSDT(Q)], in concert with correlation-consistent basis sets (
cc-pV
X
Z
,
X
=
D
, T, Q, 5, 6) that facilitate extrapolations to the complete basis set limit. The first full quartic force field of diacetylene is determined at the highly accurate all-electron CCSD(T) level with a cc-pCVQZ basis, which includes tight functions for core correlation. Application of second-order vibrational perturbation theory to our anharmonic force field yields fundamental frequencies with a mean absolute difference of only
3.9
cm
−
1
relative to the experimental band origins, without the use of any empirical scale factors. By a focal point approach, we converge on an enthalpy change for the isogyric reaction
2
H
-
C
≡
C
-
H
→
H
-
C
≡
C
-
C
≡
C
-
H
+
H
2
of (
+
0.03
,
+
0.81
)
kcal
mol
−
1
at (0, 298.15) K. With the precisely established
Δ
f
H
°
of acetylene, we thus obtain
Δ
f
H
°
(
C
4
H
2
)
=
(
109.4
,
109.7
)
±
0.3
kcal
mol
−
1
at (0, 298.15) K. Previous estimates of the diacetylene enthalpy of formation range from 102 to
120
kcal
mol
−
1
.</abstract><cop>United States</cop><pub>American Institute of Physics</pub><pmid>19191379</pmid><doi>10.1063/1.3054917</doi><tpages>1</tpages></addata></record> |
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language | eng |
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title | Enthalpy of formation and anharmonic force field of diacetylene |
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