Direct absorption spectroscopy of jet-cooled polyenes. II. The 1 1B+u←1 1A−g transitions of butadienes and hexatrienes

Leopold, D. G.; Pendley, R. D.; Roebber, J. L.; Hemley, Russell J.; Vaida, Veronica

doi:10.1063/1.447453

Cited by 158 publications

(72 citation statements)

References 52 publications

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“…The excitation energy of the planar trans-hexa-1,3,5-triene calculated with TDDFT is in a fairly good agreement with the experimental datum 70 (see Table 4). Both density functionals employed, B3LYP and BH&HLYP, predict the excitation energies within 0.3 eV from the experimental figure.…”

Section: Scheme 2: Numbering Of Atoms In Trans-135-hexatrienesupporting

confidence: 72%

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach

2008

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A time-independent density functional approach to the calculation of excitation energies from the ground states of molecules typified by the strong nondynamic electron correlation is suggested. The new method is based on the use of the spin-restricted ensemble-referenced Kohn-Sham formalism Shaik, S. Chem. Phys. Lett. 1999, 304, 429] for the calculation of the ground state. In the new method, the average energy of the ground state and a state created by a single excitation thereof is minimized with respect to the Kohn-Sham orbitals and their fractional occupation numbers. The lowest singlet excitation energies obtained with the help of the new formalism for a number of model systems, such as the hydrogen molecule with stretched bond, twisted ethylene, and twisted hexa-1,3,5-triene, are compared with the results of the timedependent density functional theory, with the results of ab initio CASSCF/CASPT2 calculations, and with the experimental data. Applicability of the new method to the description of photochemical reactions is discussed.

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Section: Scheme 2: Numbering Of Atoms In Trans-135-hexatrienesupporting

confidence: 72%

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach

2008

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“…For the first four systems ͑up to five double bonds͒, the experimental transition energies in gas phase are known. [11][12][13][14][15][16][17][18][19] Table IV reports the experimental as well as the calculated vertical transition energies. Figure 3 shows the shift in the transition energies with respect to butadiene.…”

Section: Polyenesmentioning

confidence: 99%

On the difference between the transition properties calculated with linear response- and equation of motion-CCSD approaches

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Trucks

Frisch

2009

The Journal of Chemical Physics

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Articles you may be interested in On the difference between the transition properties calculated with linear response-and equation of motion-CCSD approachesIn this work, we quantitatively investigate the difference between the linear response ͑LR͒ and the equation of motion ͑EOM͒ coupled cluster ͑CC͒ approaches in the calculation of transition properties, namely, dipole and oscillator strengths, for the most widely used truncated CC wave function, which includes single and double excitation operators. We compare systems of increasing size, where the size-extensivity may be important. Our results suggest that, for small molecules, the difference is small even with large basis sets. The difference increases with the size of the system, but it is numerically small until hundreds of electron pairs are correlated. Although these calculations may be possible in a few years, at present the EOM approach is more advantageous, albeit more approximate, because it is computationally less demanding.

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“…Similarly, in Figure 1b the calculated and measured energy gaps between the 1A g and 1B u states are plotted with experimental values. 48 First comparing the SCI/FF and SDCI/SOS calculations, we see that the power-law fits for the two are nearly parallel for the calculations of R, with the SCI/FF results approximately a factor of 2 larger in all cases. We also observe stabilization of the ground-state energy relative to SCI when DCI is included.…”

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Calculation of Ground and Excited State Polarizabilities of Unsubstituted and Donor/Acceptor Polyenes: A Comparison of the Finite-Field and Sum-Over-States Methods

1998

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In this manuscript, a relatively simple and inexpensive INDO/SCI finite-field (FF) method for calculating polarizabilities (R) is demonstrated to give good agreement with results obtained by both the INDO/MRD/ SDCI sum-over-states routine and published results using the RPA method. The FF method is as effective as the other techniques in predicting both ground and excited state R's in all substituted and unsubstituted polyenes studied. We observe the correlation described by Marder and co-workers between bond-order-alternation (BOA) and dipolar properties, such as the change in R between the ground and excited states (∆R). In addition, qualitative, but not quantitative, agreement is seen between the calculated ∆R's of polar polyenes and those measured by Stark-effect spectroscopy.Recent interest in substituted polyenes which exhibit nonlinear optical (NLO) behavior has made accurate calculations of their properties an important predictive tool in materials development. For example, the hyperpolarizabilities ( ) of molecules are of interest because this parameter is directly related to efficiency in optical frequency doubling and to the Pockel effect. Experimentally, there are two common strategies for optimizing : [1][2][3][4][5][6][7] (1) changing the donor (D) and/or acceptor (A) strength of substituents on the polyene and (2) changing the solvent polarity and/or polarizability. Both alter the local field of the polyene chain, leading to a change in bond-order alternation (BOA) 8 and in NLO properties, including . In the two-state model, 9,10 is proportional to the change in dipole moment between the ground and excited states (∆µ), so an accurate calculation of solvated ∆µ is needed to correctly model the effects of solvation on . 3,6,[11][12][13][14][15][16] In dielectric cavity models, 17 the solvent-corrected ∆µ also depends on the change in polarizability between the ground and excited states (∆R). Therefore, quantitatively accurate calculations of both ground and excited state R are needed to correctly model the solvent-effects on and ∆µ, particularly in highly polarizable systems such as the substituted polyenes. This paper compares the two most common routines for calculating ground state R, the sum-over-states and finite-field methods, and applies them to the calculation of excited state R.While techniques for the calculations of first ( ) and second (γ) order hyperpolarizabilities and ground-state polarizabilities (R g ) of polyenes are well developed, 12,14,15,[18][19][20][21][22][23] we are aware of only one example of excited-state polarizability (R e ) calculations for such systems in the literature. 24 In this published work, the random phase approximation (RPA) was utilized to investigate a series of linear, unsubstituted polyenes. Marder and coworkers have investigated trends in ∆R 25 and R g 1 with respect to BOA, but to our knowledge, no quantitative calculations of R e or ∆R have been published on substituted systems similar to those being developed for NLO applications. Because linear unsub...

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Direct absorption spectroscopy of jet-cooled polyenes. II. The 1 1B+u←1 1A−g transitions of butadienes and hexatrienes

Cited by 158 publications

References 52 publications

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach

On the difference between the transition properties calculated with linear response- and equation of motion-CCSD approaches

Calculation of Ground and Excited State Polarizabilities of Unsubstituted and Donor/Acceptor Polyenes: A Comparison of the Finite-Field and Sum-Over-States Methods

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