Intramolecular interactions and nature of the lowest electronically excited states in compounds modeling the structural unit of lignin. I. Molecular form

Quantum-chemical calculations of the electronic structure of molecules of model compounds of lignin in the ground and electronically excited states have been made by the CNDO/S method. The paper gives results on the energies and strengths of the oscillators of the electronic transitions and on the type of excited singlet and triplet states, shows the main configurations of the HOMOs and LUMOs participating in the transitions and their energies and statistical weights, and gives the distribution of charges and their redistribution on the passage of the molecules from the ground into the excited states. Donor-acceptor interactions in the molecules under investigation are discussed on the basis of the results obtained.Siberian Scientific-Research Institute of Pulp and Board, Bratsk. A. A. Zhdanov Irkutsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 265–274, March–April, 1988.     

An application of second-order n-electron valence state perturbation theory to the calculation of excited states

n–electron valence state perturbation theory (NEVPT) is a form of multireference perturbation theory where all the zero-order wave functions are of multireference nature, being generated as eigenfunctions of a two–electron model Hamiltonian. The absence of intruder states makes NEVPT an interesting choice for the calculation of electronically excited states. Test calculations have been performed on several valence and Rydberg transitions for the formaldehyde and acetone molecules; the results are in good accordance with the best calculations and with the existing experimental data.Contribution to the Jacopo Tomasi Honorary Issue     

Chemiluminescence accompanying the thermal decomposition of diethoxy(tert-butyl hydroperoxidato) aluminum

Conclusions The thermolysis of diethoxy(tert-butyl peroxide) aluminum takes place with the formation of products in electronically excited states without the participation of free radicals. One of the emitters of luminescence is acetaldehyde.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 524–528, March, 1988.     

Autocatalytic processes during oxidation of lignin in alkaline media

Results are presented that characterize features of the oxidation of lignin in alkaline media. The prerequisites are considered and proofs are given of the appearance of autocatalytic reactions on the oxidation of lignin at the level of one-electron transfer between the phenoxyl radicals being formed and the initial fragments and between chromophores in triplet electronically excited states and other fragments and of the development of concerted oxidation reactions through the appearance of active forms of oxygen, and vibrationally excited states. The results obtained indicate that on the oxidation of lignin in alkaline media a network of chemical reactions bearing the autocatalytic nature of chain processes with degenerate energy branching is formed.Siberian Scientific Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 426–433, May–June, 1988.     

Low-energy resonance states upon electron capture by five-membered heterocycles and cyclopentadiene

New resonance states were discovered for the negative molecular ions of thiophene and selenophene and a series of resonances was found for various heterocyclic compounds in the region 3.0–3.6 eV. The low-energy resonances at 1.65–2.3 eV are formed by a resonance mechanism of a form of the molecular ground state, while an electronically excited Feschbach resonance is responsible for the series of resonance states at 3.0–3.6 eV. The mother state for the latter resonance states is the first triplet state of these molecules. The first triplet state of selenophene is at 3.6±0.15 eV.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 925–927, April, 1990.     

Intramolecular interactions,orbital nature of electronic states,and lulinescence-spectroscopic properties of the phenoxasiline molecule

The electronic structure of the phenoxasiline (POS) molecule in the ground and electronically excited states has been calculated in the framework of the CNDO/S-CI method in sp and spd basis sets. The orbital nature of the S₁ and T₁ states and some luminescence-spectroscopic properties of POS have been determined theoretically and experimentally, and the influence of the l electrons of the oxygen atom and the d AO's of the silicon atom, as well as the geometry of the molecule, on them has been analyzed.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 22, No. 5, pp. 626–632, September–October, 1986.     

The Nature of Electronically Excited States and Photoprocesses in Psoralen Molecules and Their Complexes

The nature of electronically excited states of molecules of psoralens and their complexes with methanol and the photoprocesses occurring in the molecules under exposure to light were studied by quantum chemistry methods. It was found that the principal deactivation pathway for all of the compounds examined is intersystem (S–T) crossing, which substantially affects their properties as sensitizers. It was shown that isomerization and substitution of the methoxy group do not lead to significant enhancement of the S–T transition.     

A compact model system for electron–phonon calculations in discotic materials

Electron–phonon coupling underlies the unwanted rapid relaxation of electrically excited states in potential organic solar-cell materials. A compact model for the vibrational dynamics of 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) is derived from the combined use of inelastic neutron scattering (INS) spectroscopy and first-principles calculations. Because this model reproduces the essential features of the vibrational dynamics and electronic structure on the aromatic core of HAT6 it can be used as a basis for future calculations of the relaxation mechanisms of the electronically excited states.     

Electronic structure of the two isomers of the anionic form of p-coumaric acid chromophore

A theoretical study of the electronic structure of the photoactive yellow protein (PYP) model chromophore, para-coumaric acid (p-CA), is presented. Electronically excited states of the phenolate and carboxylate isomers of the deprotonated p-CA are characterized by high-level ab initio methods including state-specific and multistate multireference pertrubation theory (SS-CASPT2, and MS-CASPT2), equation-of-motion coupled-cluster methods with single and double substitutions (EOM-CCSD) and with an approximate account of triple excitations (CC3). We found that the two isomers have distinctly different patterns of ionization and excitation energies. Their excitation energies differ by more than 1 eV, in contradiction to the experimental report [Rocha-Rinza et al., J. Phys. Chem. A 113, 9442 (2009)]. The calculations confirm metastable (autoionizing) character of the valence excited states of both phenolate and carboxylate isomers of p-CA(-) in the gas phase. The type of resonance is different in the two forms. In the phenolate, the excited state lies above the detachment continuum (a shape resonance), whereas in the carboxylate the excited π→π(*) state lies below the π-orbital ionization continuum, but is above the states derived from ionization from three other orbitals (Feshbach resonance). The computed oscillator strength of the bright electronic state in the phenolate is higher than in the carboxylate, in agreement with Hu?ckel's model predictions. The analysis of photofragmentation channels shows that the most probable products for the methylated derivatives of the phenolate and carboxylate forms of p-CA(-) are CH(3), CH(2)O and CH(3), CH(2)O, CO(2), respectively, thus suggesting an experimental probe that may discriminate between the two isomers.     

Assessing solvent effects on the singlet excited state lifetime of uracil derivatives: A femtosecond fluorescence upconversion study in alcohols and D2O

The excited state lifetimes of uracil, thymine and 5-fluorouracil have been measured using femtosecond UV fluorescence upconversion in various protic and aprotic polar solvents. The fastest decays are observed in acetonitrile and the slowest in aqueous solution while those observed in alcohols are intermediate. No direct correlation with macroscopic solvent parameters such as polarity or viscosity is found, but hydrogen bonding is one key factor affecting the fluorescence decay. It is proposed that the solvent modulates the relative energy of two close-lying electronically excited states, the bright ππ^* and the dark nπ^* states. This relative energy gap controls the non-radiative relaxation of the ππ^* state through a conical intersection close to the Franck–Condon region competing with the ultrafast internal conversion to the ground state. In addition, an inverse isotope effect is observed in D₂O where the decays are faster than in H₂O.     

Localization of electronic excitation and change in the direction of electrophilic substitution reactions in some phenylazoles, 2-furylazoles, and 2-thienylazole

NMR, IR, UV, and fluorescence spectral data and semiempirical quantum chemical PPP and INDO/S methods were used to refine the electronic structure of several azoles and analyze the change in course of electrophilic aromatic substitution reactions involving addition and dissociation in going from free bases to protonated forms. The electronically excited singlet and triplet states of the protonated forms of the mono- and bicyclic systems studied feature excitation localization different from the free molecules. The results of quantum chemical modelling of the change in the reactivities of these systems are given.Dedicated to Prof. A. Katritzky on his seventieth birthday.Russian International Friendship University, 117302 Moscow. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1181–1194, September, 1998.     

Resonant electron trapping and photoelectron spectroscopy for substituted fluorinated nitrobenzenes

Mass spectra have been recorded for dissociative electron capture DEC negative ions together with photoelectron spectra for the molecules of fluorinated nitrobenzenes. Nitrobenzene DEC is governed in the main by orbitals having appreciable contributions from the nitro group atoms. Resonant states are formed in the molecular negative fluoronitrobenzene ions via the Feshbach electronically excited resonance mechanism, which involves the excitation of an electron from a series of filled MO to several vacant MO.Chemical Institute, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 6, pp. 683–688, November–December, 1991. Original article submitted November 27, 1989.     

乙酰基的电子激发态

对乙酰基的基态（X12A′）和激发态进行了理论和实验研究。通过采用MRSDCI和MP2方法计算，获得了CH3CO自由基的四个电子激发态（A12A″，B22A′，C32A′，D22A″），其垂直激发能分别为250．8kJ·mol－1，472．3kJ·mol－1，645．8kJ·mol－1和674．7kJ·mol－1。运用时间分辨付里叶红外光谱仪（TR－FTIR）分别研究了CH3CO自由基的热解和光解反应，观察到初生产物CO（V）的红外发射光谱．势垒仅为75．2kJ·mol－1的基态CH3CO极易热解．532um的激光只能将CH3CO激发到束缚态A12A″，故未观察到CO信号；而248nm或266nm的激光可使CH3CO发生B22A′←X12A′跃迁，生成高振动激发的CO（V8）产物．     

Steps toward a high precision evaluation of the hyperfine interactions in neutral muonic helium

The solution of the Schrödinger equation of the neutral muonic helium is sketched by an eigenfunction expansion method: the eigenfunctions of the two Coulombic centres problem (of chargesZ ₁=2,Z ₂=–1) are used to expand the wave function. Our Born expansion method is a generalization of the Born-Oppenheimer approximation to a system in which the two centres (He, ^–) do not have a stable equilibrium distance. The adiabatic approximation is solved, upper-lower bounds on the eigenvalue are given for a number of states. The hyperfine energy corrections are calculated in general terms and are given numerically for the ground state and for the first muonically and electronically excited states in the frames of the adiabatic approximation. Our best value fails to give the observed hyperfine splitting of the ground state by some 5 × 10^–4 (2 MHz).     

An ab initio study of electronic spectra and excited-state properties of 7-azaindole in vapour phase and aqueous solution

The geometries of 7-azaindole (7AI), its tautomer (7AT), and 7AI–H₂O and 7AT–H₂O complexes were optimised in the ground state and some low-lying singlet excited states using the 3-21G basis set. Differences of total energies of the optimised ground and excited states and the vertical excitation energies of these systems were used to explain the observed electronic spectra. Effect of solvation of these systems in bulk water was studied using the polarized continuum model (PCM). The mode of binding of a water molecule in the S₂(n–π^*) excited state of 7AI was found to be quite different from those in its ground and π–π^* excited states. It is shown that crossing of the lowest two singlet excited-state potential surfaces S₁(π–π^*) and S₂(n–π^*) of 7AI occurs in the vapour phase under geometry relaxation while on interaction with water, the S₂(n–π^*) excited state is raised up appreciably going even above the S₃(π–π^*) excited state. Ground- and excited-state molecular electrostatic potential mapping was carried out, which led to valuable information regarding the nature of excited states of the above-mentioned systems.     

Influence of silicon coordination surrounding on the chemical structure of oxides

A comparative analysis of structural features of SiO₂ polymorphic modifications was made by Raman, and high-resolution electronic spectroscopy. It was found that the presence of isolated Si-O, Si-Si, and O-O oscillators in the ground and electronically excited states is a characteristic feature of all the structures involving silicon atoms in oxygen tetrahedral coordination surrounding. It was shown that the increase in the silicon coordination number to six (stishovite) leads to a decrease in the extent of formation of electronically excited states due to removal of barriers to the relaxation of excitation energies. This conclusion is confirmed by the low-frequency shift of the fundamental absorption and by the disappearance of the high-frequency anomaly (Si-O) and characteristic lines of Si-Si oscillators.     

Heteroatom Effects on Electronic Excited State Hydrogen Bonding of Fluorenone‐Based Molecular Materials

In this work, the geometry optimizations in the ground state and electronic excitation energies and corresponding oscillation strengths of the low‐lying electronically excited states for the isolated fluorenone (FN) and FN‐based molecular monomers, the relatively hydrogen‐bonded dimers, and doubly hydrogen‐bonded trimers, are calculated by the density functional theory and time‐dependent density functional theory methods, respectively. We find the intermolecular hydrogen bond CO···H O is strengthened in some of the electronically excited states of the hydrogen‐bonded dimers and doubly hydrogen‐bonded trimers, because the excitation energy in a related excited state decrease and electronic spectral redshift are induced. Similarly, the hydrogen bond CO···H O is weakened in other excited states. On this basis, owing to the important difference of electronegativity, heteroatoms S, Se, and Te that substitute for the O atom in the carbonyl group of the FN molecule have a significant effect on the strength of the hydrogen bond and the spectral shift. It is observed that the hydrogen bond CTe···H O is too weak to be formed. When the CS and CSe substitute for CO, the strength of the hydrogen bonds and electronic spectra frequency shift are significantly changed in the electronic excited state due to the electron transition type transformation from the ππ* feature to σπ* feature. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:153–162, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21075     

Time-dependent Density Functional Theory Study on the Electronically Excited States of N-Methylformamide in Aqueous Solution

Excited-state hydrogen-bonding dynamics of N-methylformamide (NMF) in water has been investigated by time-dependent density functional theory (TDDFT) method. The ground-state geometry optimizations were calculated by density functional theory (DFT) method, while the electronic transition energies and corresponding oscillation strengths of the low-lying electronically excited states of isolated NMF, water monomers and the hydrogen-bonded NMF-H 2 O were calculated by TDDFT method. According to Zhao's rule on the excited-state hydrogen bonding dynamics, our results demonstrate that the intermolecular hydrogen bond C=O···O-H is strengthened and weakened in different electronically excited states. The hydrogen bond strengthening and weakening in the electronically excited state plays an important role in the photophysics of NMF in solutions.     

Semiempirical NDDO/MC calculations of the excited states of the chromate ion

A new semiempirical method of calculating the excited states of transition metal complexes is developed. This technique uses the configuration interaction and semiempirical NDDO/MC methods to obtain the ground state of a set of Slater type valence spd-orbitals chosen from the optical spectra of transition metals together with the corresponding core integrals. The method is tested in calculations of the electronically excited states of the chromate ion. Good agreement with the experimental energies of vertical transitions and the results of ab initio calculations is achieved.     

Thermoemission of singlet oxygen and chemical structure of copper oxides

Thermal treatment of copper oxides (CuO, Cu₂O) is accompanied by large-scale emission of singlet oxygen molecules (¹Σ⁺ _g ). Electron spectroscopy for chemical analysis (ESCA) and electronic and IR spectroscopy were used to show that the thermoemission of electronically excited molecules results from dark generation of electronically excited states which contain in their structure isolated metal-metal bonds and oxygen associates. The anomalous diamagnetic response of the samples and reduced thermoemission activity (Cu₂O) are associated with cooperative interaction of electronically excited states.