FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2950554402> ?p ?o ?g. }

• W2950554402 endingPage "6280" @default.
• W2950554402 startingPage "6269" @default.
• W2950554402 abstract "The 4H-pyran-4-one (4PN) molecule serves as a model for investigating structural changes following π* ← n electronic excitation. We have recorded the cavity ringdown (CRD) absorption spectrum of 4PN vapor at room temperature, over the wavelength region from 350 to 370 nm. This spectral region includes the T1(n,π*) ← S0 band system as well as the low-energy portion of the S1(n,π*) ← S0 system. Aided by predictions from ab initio (equation-of-motion excitation energies with dynamical correlation incorporated at the level of coupled cluster singles doubles, EOM-EE-CCSD) and density functional theory (time-dependent density functional theory with PBE0 functional, TDPBE0) calculations, we have made vibronic assignments for about 30 features in the CRD spectrum, mostly T1(n,π*) ← S0 transitions. We have used these results to correct certain vibronic assignments appearing in the previous literature for both T1(n,π*) ← S0 and S1(n,π*) ← S0 band systems. We conclude that the lowest-energy carbonyl wagging fundamentals (ν27, in-plane and ν17, out-of-plane) undergo significant frequency drops (28 and 50%, respectively) upon T1(n,π*) ← S0 excitation and similar drops (29 and 39%, respectively) for S1(n,π*) ← S0 excitation. We find that vibrational modes involving the conjugated ring atoms undergo relatively small frequency changes upon π* ← n excitation, for both T1 and S1 states. We have used the present spectroscopic results and vibronic assignments to test the accuracy of computed excited-state frequencies for 4PN. This benchmarking process shows that the economical time-dependent density functional theory method is impressively accurate for certain (but not all) vibrational modes. The highly correlated EOM-EE-CCSD ab initio method is capable of making accurate frequency predictions, but the results, unexpectedly, depend sensitively on basis set family. This anomaly is traceable to a computed conical intersection between the T1(n,π*) and T2(π,π*) surfaces near the T1(n,π*) potential minimum. Relatively small errors in the location of the conical intersection lead to enhanced mixing of the two electronic states and incorrect T1(n,π*) vibrational frequencies when certain triple-ζ quality basis sets are used." @default.
• W2950554402 created "2019-06-27" @default.
• W2950554402 creator A5008508408 @default.
• W2950554402 creator A5019964750 @default.
• W2950554402 creator A5034071834 @default.
• W2950554402 creator A5034569493 @default.
• W2950554402 date "2019-06-18" @default.
• W2950554402 modified "2023-09-27" @default.
• W2950554402 title "Triplet and Singlet (n,π*) Excited States of 4<i>H</i>-Pyran-4-one Characterized by Cavity Ringdown Spectroscopy and Quantum-Chemical Calculations" @default.
• W2950554402 cites W1538516187 @default.
• W2950554402 cites W1964373787 @default.
• W2950554402 cites W1969106313 @default.
• W2950554402 cites W1975599353 @default.
• W2950554402 cites W1980617992 @default.
• W2950554402 cites W1982356449 @default.
• W2950554402 cites W1991674923 @default.
• W2950554402 cites W1994007662 @default.
• W2950554402 cites W1994305427 @default.
• W2950554402 cites W1999738322 @default.
• W2950554402 cites W2008423326 @default.
• W2950554402 cites W2009066586 @default.
• W2950554402 cites W2023271753 @default.
• W2950554402 cites W2056967289 @default.
• W2950554402 cites W2066481445 @default.
• W2950554402 cites W2069006374 @default.
• W2950554402 cites W2083171749 @default.
• W2950554402 cites W2087306996 @default.
• W2950554402 cites W2100949693 @default.
• W2950554402 cites W2591829650 @default.
• W2950554402 doi "https://doi.org/10.1021/acs.jpca.9b04238" @default.
• W2950554402 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/31298545" @default.
• W2950554402 hasPublicationYear "2019" @default.
• W2950554402 type Work @default.
• W2950554402 sameAs 2950554402 @default.
• W2950554402 citedByCount "4" @default.
• W2950554402 countsByYear W29505544022019 @default.
• W2950554402 countsByYear W29505544022020 @default.
• W2950554402 countsByYear W29505544022022 @default.
• W2950554402 countsByYear W29505544022023 @default.
• W2950554402 crossrefType "journal-article" @default.
• W2950554402 hasAuthorship W2950554402A5008508408 @default.
• W2950554402 hasAuthorship W2950554402A5019964750 @default.
• W2950554402 hasAuthorship W2950554402A5034071834 @default.
• W2950554402 hasAuthorship W2950554402A5034569493 @default.
• W2950554402 hasConcept C121332964 @default.
• W2950554402 hasConcept C147597530 @default.
• W2950554402 hasConcept C152365726 @default.
• W2950554402 hasConcept C178790620 @default.
• W2950554402 hasConcept C181500209 @default.
• W2950554402 hasConcept C184779094 @default.
• W2950554402 hasConcept C185592680 @default.
• W2950554402 hasConcept C19637589 @default.
• W2950554402 hasConcept C20853536 @default.
• W2950554402 hasConcept C2781442258 @default.
• W2950554402 hasConcept C32891209 @default.
• W2950554402 hasConcept C32909587 @default.
• W2950554402 hasConcept C33062035 @default.
• W2950554402 hasConcept C41999313 @default.
• W2950554402 hasConcept C62520636 @default.
• W2950554402 hasConcept C83581075 @default.
• W2950554402 hasConceptScore W2950554402C121332964 @default.
• W2950554402 hasConceptScore W2950554402C147597530 @default.
• W2950554402 hasConceptScore W2950554402C152365726 @default.
• W2950554402 hasConceptScore W2950554402C178790620 @default.
• W2950554402 hasConceptScore W2950554402C181500209 @default.
• W2950554402 hasConceptScore W2950554402C184779094 @default.
• W2950554402 hasConceptScore W2950554402C185592680 @default.
• W2950554402 hasConceptScore W2950554402C19637589 @default.
• W2950554402 hasConceptScore W2950554402C20853536 @default.
• W2950554402 hasConceptScore W2950554402C2781442258 @default.
• W2950554402 hasConceptScore W2950554402C32891209 @default.
• W2950554402 hasConceptScore W2950554402C32909587 @default.
• W2950554402 hasConceptScore W2950554402C33062035 @default.
• W2950554402 hasConceptScore W2950554402C41999313 @default.
• W2950554402 hasConceptScore W2950554402C62520636 @default.
• W2950554402 hasConceptScore W2950554402C83581075 @default.
• W2950554402 hasFunder F4320337393 @default.
• W2950554402 hasIssue "29" @default.
• W2950554402 hasLocation W29505544021 @default.
• W2950554402 hasLocation W29505544022 @default.
• W2950554402 hasOpenAccess W2950554402 @default.
• W2950554402 hasPrimaryLocation W29505544021 @default.
• W2950554402 hasRelatedWork W1659354898 @default.
• W2950554402 hasRelatedWork W1972686187 @default.
• W2950554402 hasRelatedWork W2023038967 @default.
• W2950554402 hasRelatedWork W2031965011 @default.
• W2950554402 hasRelatedWork W2082494576 @default.
• W2950554402 hasRelatedWork W3043639618 @default.
• W2950554402 hasRelatedWork W4220862459 @default.
• W2950554402 hasRelatedWork W4231256999 @default.
• W2950554402 hasRelatedWork W4239270715 @default.
• W2950554402 hasRelatedWork W835392705 @default.
• W2950554402 hasVolume "123" @default.
• W2950554402 isParatext "false" @default.
• W2950554402 isRetracted "false" @default.
• W2950554402 magId "2950554402" @default.
• W2950554402 workType "article" @default.