Development and assessment of new exchange-correlation functionals

Hamprecht, Fred A.; Cohen, Aron J.; Tozer, David J.; Handy, Nicholas C.

doi:10.1063/1.477267

Cited by 1,410 publications

(998 citation statements)

References 31 publications

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“…Therefore, we suggest that adsorption studies on the hydroxylated surface should employ PBE with an 18-layer surface slab. The best overall hybrid functional for hydrogen bonded systems is B3P86, 30 although mPWB1K 49 and B97-1 50 perform similarly well. The latter two functionals provide more accurate activation energies 30, 31 and their future implementation in CRYSTAL would provide an accurate method for describing reactions on the hydroxylated surface of quartz.…”

Section: Hydroxylated Surfacementioning

confidence: 99%

Structure and stability of the (001) α-quartz surface

Goumans

Wander

Brown

et al. 2007

Phys. Chem. Chem. Phys.

203

222

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Structure and stability of the (001) alpha-quartz surface Article (Published Version) http://sro.sussex.ac.uk Goumans, T P M, Wander, Adrian, Brown, Wendy A and Catlow, C Richard A (2007) Structure and stability of the (001) alpha-quartz surface. Physical Chemistry Chemical Physics, 9 (17). 2146 -2152 . ISSN 1463 This version is available from Sussex Research Online: http://sro.sussex.ac.uk/48679/ This document is made available in accordance with publisher policies and may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the URL above for details on accessing the published version. Copyright and reuse:Sussex Research Online is a digital repository of the research output of the University.Copyright and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable, the material made available in SRO has been checked for eligibility before being made available.Copies of full text items generally can be reproduced, displayed or performed and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way.Structure and stability of the (001) The structure and surface energies of the cleaved, reconstructed, and fully hydroxylated (001) a-quartz surface of various thicknesses are investigated with periodic density functional theory (DFT). The properties of the cleaved and hydroxylated surface are reproduced with a slab thickness of 18 atomic layers, while a thicker 27-layer slab is necessary for the reconstructed surface. The performance of the hybrid DFT functional B3LYP, using an atomic basis set, is compared with the generalised gradient approximation, PBE, employing plane waves. Both methodologies give similar structures and surface energies for the cleaved and reconstructed surfaces, which validates studying these surfaces with hybrid DFT. However, there is a slight difference between the PBE and B3LYP approach for the geometry of the hydrogen bonded network on the hydroxylated surface. The PBE adsorption energy of CO on a surface silanol site is in good agreement with experimental values, suggesting that this method is more accurate for hydrogen bonded structures than B3LYP. New hybrid functionals, however, yield improved weak interactions. Since these functionals also give superior activation energies, we recommend applying the new functionals to contemporary issues involving the silica surface and adsorbates on this surface.

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Section: Hydroxylated Surfacementioning

confidence: 99%

Structure and stability of the (001) α-quartz surface

Goumans

Wander

Brown

et al. 2007

Phys. Chem. Chem. Phys.

203

222

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“…Orbitals for the ground state wavefunctions of styrene and the styrene cation (calculated at the DFT HCTH/6-311+G* level) are the reference orbitals for the TDDFT HCTH/6-311+G* excited state calculations [32][33] and are presented in figure 2. The resulting configurations and weights of the excited state wavefunctions for styrene and the styrene cation are summarized in tables 1(a) and (b).…”

Section: Theorymentioning

confidence: 99%

“…The TDDFT theory is used here to calculate the electronic state configuration and the correlations between the excited states of the neutral molecule and the cation as described below. The asymptotically corrected HCTH functional [32][33] was chosen as it was found to give reliable excitation energies for benzene. 34 (a) Energy (eV) Excitation configuration from S 0 Coefficient Weight S 1 4.31 7 One-electron ionisation correlations can be determined by inspection of tables 1(a) and (b).…”

Section: Theorymentioning

confidence: 99%

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

Nunn

Minns

Spesyvtsev

et al. 2010

Phys. Chem. Chem. Phys.

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We report a femtosecond time-resolved photoelectron spectroscopy (TRPES) investigation of internal conversion in the first two excited singlet electronic states of styrene. We find that radiationless decay through an S 1 /S 0 conical intersection occurs on a timescale of ~4 ps following direct excitation to S 1 with 0.6 eV excess energy, but that the same process is significantly slower (~20 ps) if it follows internal conversion from S 2 to S 1 after excitation to S 2 with 0.3 eV excess energy (0.9 eV excess energy in S 1 ).

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“…The geometries of the investigated amino acids conformers were obtained by DFT computations using the B97-1 functional [14] with the cc-pVDZ correlation consistent basis set. Relative energies were obtained at HF, MP2 and DFT-B97-1 levels using cc-pVDZ and aug-cc-pVDZ basis sets, and were corrected for zero-point vibrational energy (ZPVE)…”

Section: Computational Proceduresmentioning

confidence: 99%

Electronic and vibrational polarizabilities of the twenty naturally occurring amino acids

Millefiori

Alparone

Millefiori

et al. 2008

Biophysical Chemistry

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The geometries, relative energies, gas-phase static and dynamic dipole polarizabilities of the two most stable neutral forms and of the zwitterionic form of the twenty naturally occurring amino acids have been obtained by Density Functional and conventional ab initio HatreeFock theories using correlation consistent basis sets. Mean electronic polarizabilities (<α e >s) are encompassed in the 40-160 a.u. range and are little dependent on the amino acid framework conformation, structure and conformation. The relation between <α e > and the number of electrons in the molecule makes to classify the amino acids as one of the most polarizable family of compounds. Calculated <α e > values of the neutral forms linearly relate to the molecular volume and molecular hardness as well as, rather unexpectedly, with the experimental values in water solution, where amino acids are known to be in a zwitterionic form. Vibrational polarizabilities amount to 15-45 a.u.. They come essentially from the lowfrequency angular deformation modes of the -OH and -NH 2 groups.

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Development and assessment of new exchange-correlation functionals

Cited by 1,410 publications

References 31 publications

Structure and stability of the (001) α-quartz surface

Structure and stability of the (001) α-quartz surface

Ultrafast dynamics through conical intersections and intramolecular vibrational energy redistribution in styrene

Electronic and vibrational polarizabilities of the twenty naturally occurring amino acids

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