Vertical ionization potentials of ethylene: the right answer for the right reason?

Yau, Anthony D.; Perera, S. Ajith; Bartlett, Rodney J.

doi:10.1080/00268970110097848

Cited by 28 publications

(10 citation statements)

References 43 publications

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“…The current composite values are in reasonably good agreement with the coupled cluster theory IPs reported by Yau et al 146 They performed all-electron calculations on the five lowest cation states ( 2 B 3u , 2 B 3g , 2 A g , 2 B 2u , and 2 B 1u in D 2h symmetry) with cc-pVDZ through cc-pVQZ basis sets, followed by CBS extrapolation with an exponential 88 and 1/ 3 max formulas. Differences attributable to the choice of extrapolation formula were small.…”

Section: Ionization Potentialssupporting

confidence: 88%

“…i Hasegawa et al 147 Based on SAC-CI (General-R) calculations employing a [5s3p1d/3s1p] + bond centered (spd) function basis set. j Desjardins et al 41 146 Their best frozen core VIP( 2 B 3u ) estimate obtained with IP-EOM-CCSDT was 10.75 eV in exact agreement with our own value, which contains a small CV correction.…”

Section: Ionization Potentialssupporting

confidence: 87%

“…Differences attributable to the choice of extrapolation formula were small. Yau's exponential 146 Based on a complete basis set extrapolation of cc-pVTZ and cc-pVQZ basis set energies using a 1/ max 3 formula suggested by Bak et al 155 All electrons were correlated. An exponential extrapolation 88 of cc-pVDZ through cc-pVQZ energies yields a similar VIP of 10.7 eV.…”

Section: Ionization Potentialsmentioning

confidence: 99%

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A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

Feller

Peterson

Davidson

2014

The Journal of Chemical Physics

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A systematic sequence of configuration interaction and coupled cluster calculations were used to describe selected low-lying singlet and triplet vertically excited states of ethylene with the goal of approaching the all electron, full configuration interaction/complete basis set limit. Included among these is the notoriously difficult, mixed valence/Rydberg (1)B(1u) V state. Techniques included complete active space and iterative natural orbital configuration interaction with large reference spaces which led to variational spaces of 1.8 × 10(9) parameters. Care was taken to avoid unintentionally biasing the results due to the widely recognized sensitivity of the V state to the details of the calculation. The lowest vertical and adiabatic ionization potentials to the (2)B(3u) and (2)B3 states were also determined. In addition, the heat of formation of twisted ethylene (3)A1 was obtained from large basis set coupled cluster theory calculations including corrections for core/valence, scalar relativistic and higher order correlation recovery.

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Section: Ionization Potentialssupporting

confidence: 88%

Section: Ionization Potentialssupporting

confidence: 87%

Section: Ionization Potentialsmentioning

confidence: 99%

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A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

Feller

Peterson

Davidson

2014

The Journal of Chemical Physics

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“…1(a), the electron configuration of the HOMO ð1b 3u Þ orbital is a π state whose electron density is dominantly distributed perpendicular to the molecular plane, whereas that of the HOMO-1 ð1b 3g Þ orbital is mainly distributed along the C-H bond directions and that of the HOMO-2 ð3a g Þ orbital along the C-C bond. The vertical ionization potentials of removing one electron from these orbitals were predicted to be 10.8 eV (HOMO), 13.2 eV (HOMO-1), and 15.0 eV (HOMO-2) [34]. The double ionization potential of ethylene into the ground ionic state of the ethylene dication is 29.46 eV [35].…”

Section: Resultsmentioning

confidence: 99%

Electronic Predetermination of Ethylene Fragmentation Dynamics

et al. 2014

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We experimentally investigate the dependence of the fragmentation behavior of the ethylene dication on the intensity and duration of the laser pulses that initiate the fragmentation dynamics by strong-field double ionization. Using coincidence momentum imaging for the detection of ionic fragments, we disentangle the different contributions of ionization from lower-valence orbitals and field-driven excitation dynamics to the population of certain dissociative excited ionic states that are connected to one of several possible fragmentation pathways towards a given set of fragment ions. We find that the excitation probability to a particular excited state and therewith the outcome of the fragmentation reaction strongly depend on the parameters of the laser pulse. This, in turn, opens up new possibilities for controlling the outcome of fragmentation reactions of polyatomic molecules in that it may allow one to selectively enhance or suppress individual fragmentation channels, which was not possible in previous attempts of controlling fragmentation processes of polyatomic molecules with strong laser fields.

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“…Accurate description of ionized states with open-shell character presents a challenge for quantum chemistry [38,39,45]. Standard single-reference methods based on unrestricted Hartree-Fock (UHF) references, e.g., UMP2, suffer from spin-contamination and tend to overestimate charge localization [39].…”

Section: A Computational Methodsmentioning

confidence: 99%

Electronic Structure and Spectroscopy of Nucleic Acid Bases: Ionization Energies, Ionization-Induced Structural Changes, and Photoelectron Spectra

et al. 2010

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We report high-level ab initio calculations and single-photon ionization mass spectrometry study of ionization of adenine (A), thymine (T), cytosine (C) and guanine (G). For thymine and adenine, only the lowest-energy tautomers were considered, whereas for cytosine and guanine we characterized five lowest-energy tautomeric forms. The first adiabatic and several vertical ionization energies were computed us-

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Vertical ionization potentials of ethylene: the right answer for the right reason?

Cited by 28 publications

References 43 publications

A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

A systematic approach to vertically excited states of ethylene using configuration interaction and coupled cluster techniques

Electronic Predetermination of Ethylene Fragmentation Dynamics

Electronic Structure and Spectroscopy of Nucleic Acid Bases: Ionization Energies, Ionization-Induced Structural Changes, and Photoelectron Spectra

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