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4.5 Chapter 4 references
[1] K. Kowalski and P. Piecuch. The active-space equation-of-motion coupled-cluster
methods for excited electronic states: The EOMCCSDt approach. J. Chem. Phys.,
113(19):8490–8502, 2000.
[2] K. Kowalski and P. Piecuch. The active-space equation-of-motion coupled-cluster
methods for excited electronic states: Full EOMCCSDt. J. Chem. Phys.,
115(2):643–651, 2001.
[3] L.V. Slipchenko and A.I. Krylov. Spin-conserving and spin-flipping equation-of-
motion coupled-cluster method with triple excitations. J. Chem. Phys.,
123:084107–084120, 2005.
[4] P. Piecuch, K. Kowalski, I.S.O. Pimienta, and M.J. Mcguire. Recent advances
in electronic structure theory: Method of moments of coupled-cluster equations
and renormalized coupled-cluster approaches. Int. Rev. Phys. Chem., 21:527–665,
2002.
[5] K. Kowalski and P. Piecuch. New coupled-cluster methods with singles, doubles,
and noniterative triples for high accuracy calculations of excited electronic states.
J. Chem. Phys., 120:1715–1738, 2004.
[6] Y. He, C. Wu, and W. Kong. Photophysics of methyl-substituted uracils and
thymines and their water complexes in the gas phase. J. Phys. Chem. A, 108:943–
949, 2004.
[7] H. Larsen, K. Hald, J. Olsen, and P. Jørgensen. Triplet excitation energies in full
configuration interaction and coupled-cluster theory. J. Chem. Phys., 115:3015–
3020, 2001.
[8] A.D. Becke. Density-functional thermochemistry. iii. The role of exact exchange.
J. Chem. Phys., 98:5648, 1993.
[9] R. Krishnan, J.S. Binkley, R. Seeger, and J.A. Pople. Self-consistent molecular
orbital methods. XX. A basis set for correlated wave functions. J. Chem. Phys.,
72:650, 1980.
[10] T. Clark, J. Chandrasekhar, and P.V.R. Schleyer. Efficient diffuse function-augmented
basis sets for anion calculations. III. The 3-21+g basis set for first-row
elements, li-f. J. Comput. Chem., 4:294–301, 1983.
129
Object Description
| Title | Development of predictive electronic structure methods and their application to atmospheric chemistry, combustion, and biologically relevant systems |
| Author | Epifanovskiy, Evgeny |
| Author email | epifanov@usc.edu; epifanov@usc.edu |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry |
| School | College of Letters, Arts and Sciences |
| Date defended/completed | 2011-03-21 |
| Date submitted | 2011 |
| Restricted until | Unrestricted |
| Date published | 2011-04-28 |
| Advisor (committee chair) | Krylov, Anna I. |
| Advisor (committee member) |
Wittig, Curt Johnson, Clifford |
| Abstract | This work demonstrates electronic structure techniques that enable predictive modeling of the properties of biologically relevant species. Chapters 2 and 3 present studies of the electronically excited and detached states of the chromophore of the green fluorescent protein, the mechanism of its cis-trans isomerization, and the effect of oxidation. The bright excited ππ∗ state of the chromophore in the gas phase located at 2.6 eV is found to have an autoionizing resonance nature as it lies above the electron detachment level at 2.4 eV. The calculation of the barrier for the ground-state cis-trans isomerization of the chromophore yields 14.8 kcal/mol, which agrees with an experimental value of 15.4 kcal/mol; the electronic correlation and solvent stabilization are shown to have an important effect. In Chapter 3, a one-photon two-electron mechanism is proposed to explain the experimentally observed oxidative reddening of the chromophore. Chapter 4 considers the excited states of uracil. It demonstrates the role of the one-electron basis set and triples excitations in obtaining the converged values of the excitation energies of the nπ∗ and ππ∗ states. The effects of the solvent and protein environment are included in some of the models.; Chapter 5 describes an implementation of the algorithm for locating and exploring intersection seams between potential energy surfaces. The theory is illustrated with examples from atmospheric and combustion chemistry. |
| Keyword | electronic structure theory; coupled clusters theory; equation of motion theory; organic chromophore; green fluorescent protein; uracil |
| Language | English |
| Part of collection | University of Southern California dissertations and theses |
| Publisher (of the original version) | University of Southern California |
| Place of publication (of the original version) | Los Angeles, California |
| Publisher (of the digital version) | University of Southern California. Libraries |
| Provenance | Electronically uploaded by the author |
| Type | texts |
| Legacy record ID | usctheses-m3801 |
| Contributing entity | University of Southern California |
| Rights | Epifanovskiy, Evgeny |
| Repository name | Libraries, University of Southern California |
| Repository address | Los Angeles, California |
| Repository email | cisadmin@lib.usc.edu |
| Filename | etd-Epifanovskiy-4557 |
| Archival file | uscthesesreloadpub_Volume14/etd-Epifanovskiy-4557.pdf |
Description
| Title | Page 139 |
| Contributing entity | University of Southern California |
| Repository email | cisadmin@lib.usc.edu |
| Full text | 4.5 Chapter 4 references [1] K. Kowalski and P. Piecuch. The active-space equation-of-motion coupled-cluster methods for excited electronic states: The EOMCCSDt approach. J. Chem. Phys., 113(19):8490–8502, 2000. [2] K. Kowalski and P. Piecuch. The active-space equation-of-motion coupled-cluster methods for excited electronic states: Full EOMCCSDt. J. Chem. Phys., 115(2):643–651, 2001. [3] L.V. Slipchenko and A.I. Krylov. Spin-conserving and spin-flipping equation-of- motion coupled-cluster method with triple excitations. J. Chem. Phys., 123:084107–084120, 2005. [4] P. Piecuch, K. Kowalski, I.S.O. Pimienta, and M.J. Mcguire. Recent advances in electronic structure theory: Method of moments of coupled-cluster equations and renormalized coupled-cluster approaches. Int. Rev. Phys. Chem., 21:527–665, 2002. [5] K. Kowalski and P. Piecuch. New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states. J. Chem. Phys., 120:1715–1738, 2004. [6] Y. He, C. Wu, and W. Kong. Photophysics of methyl-substituted uracils and thymines and their water complexes in the gas phase. J. Phys. Chem. A, 108:943– 949, 2004. [7] H. Larsen, K. Hald, J. Olsen, and P. Jørgensen. Triplet excitation energies in full configuration interaction and coupled-cluster theory. J. Chem. Phys., 115:3015– 3020, 2001. [8] A.D. Becke. Density-functional thermochemistry. iii. The role of exact exchange. J. Chem. Phys., 98:5648, 1993. [9] R. Krishnan, J.S. Binkley, R. Seeger, and J.A. Pople. Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J. Chem. Phys., 72:650, 1980. [10] T. Clark, J. Chandrasekhar, and P.V.R. Schleyer. Efficient diffuse function-augmented basis sets for anion calculations. III. The 3-21+g basis set for first-row elements, li-f. J. Comput. Chem., 4:294–301, 1983. 129 |
