Electronic structure of benzaldehyde: A comparative study of the lowest excited singlet π* ← π and π* ← n states

VE-PPP, CNDO/2, and CNDO/s-CI methods have been used to investigate the electronic spectrum and structure of benzaldehyde. Electronic charge distributions and bond orders in the ground and lowest excited singlet π* ← π and π* ← n states of the molecule have been studied. The molecule has been shown to be nonplanar in the lowest π* ← n excited singlet state, in agreement with the conclusions drawn from the study of vibrational spectra. Dipole moments in both excited states have been shown to be larger than the ground-state value. Thus, the ambiguity in the experimental result for the π* ← π n excited singlet state dipole moment has been resolved. It has been shown that the n orbital is mainly localized on the CHO group. Furthermore, charge distributions, dipole moments, and molecular geometries are shown to be very different in the excited singlet π* ← π and π* ← n states.     

Vibrational structure of the electron transition to the second excited singlet state of pyridine N-oxide

The vibrational structure of the electron transition to the second singlet excited state of pyridine N-oxide has been studied. The frequency of the 0–0 transition is 34502 cm⁻¹. A computer-aided technique for the assignment of the frequencies of the normal vibrations of polyatomic molecules in the excited electronic states is proposed. The frequencies of the totally symmetric vibrations of pyridine N-oxide in the second singlet electronically excited state are assigned. N. G. Chernyshevskii Saratov State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 36, No. 2, pp. 350–355, March–April, 1995. Translated by I. Izvekova     

Low‐lying singlet excited states of isocyanogen

Recent photofragment fluorescence excitation (PHOFEX) spectroscopy experiments have observed the ùA″ singlet excited state of isocyanogen (CNCN) for the first time. The observed spectrum is not completely assigned and significant questions remain about the excited states of this system. To provide insight into the energetically accessible excited states of CNCN, optimized geometries, harmonic vibrational frequencies, and excitation energies for the first three singlet excited states are determined using equation‐of‐motion coupled‐cluster theory with singles and doubles (EOM‐CCSD) and correlation‐consistent basis sets. Additionally, excited state coupled‐cluster methods which approximate the contributions from triples (CC3) are utilized to estimate the effect of higher‐order correlation on the energy of each excited state. For the ùA″ state, our best estimate for T₀ is about 42,200 cm^?1, in agreement with the experimentally estimated upper limit for the zero‐point level of 42,523 cm^?1. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Radiationless transitions between excited singlet states of biacetyl

Emission processes from lower excited states S₁ (fluorescence) and T₁ (phosphorescence) have been studied in the gas and liquid phases when biacetyl is excited into the second singlet state S₂. (In agreement with Kasha's rule no fluorescence is observed from the S₂ state.) In the liquid phase, when biacetyl is excited into the singlet states S₁ and S₂, no difference is observed between these emission processes. This phenomenon certainly results from an efficient nonradiative transition between the second excited singlet state S₂ and the first excited state S₁ with practically no excess vibrational energy. The quantum yield of this transition is almost unity and does not depend on the nature of the solvent. In the gas phase no emission processes are observed when biacetyl is excited into the S₂ state at low pressure (less than 10 mm Hg). High pressure of inert gas is necessary in order to observe these processes. As for excitation into the S₁ state with vibrational energy, loss of vibrational energy through collisions occurs from the S₂ state. The quantum yield of the S₂ → S₁ transition by excitation at 290 nm is estimated around 0.5–0.6 at 6 atm of inert gas (ethane, ethylene, or carbon dioxide).     

Butterfly motion of the isolated pentacene molecule in its first-excited singlet state

The energetics and the energy-resolved decay of the S₁(¹B_2u) electronically excited state of the pentacene molecule in seeded supersonic beams has been investigated. Two low-frequency, intense spectral features located at excess vibrational energies of 77 cm^?1 and 202 cm^?1 above the origin were observed, and provide spectroscopic evidence for the quasiplanarity of the isolated pentacene molecule in its first-excited singlet state.     

1,1‐Dilithioethylene: Toward Spectroscopic Identification of the Definitive Singlet Ground Electronic State of a Peculiar Structure

1,1‐Dilithioethylene is a prototypical carbon–lithium compound that is not known experimentally. All low‐lying singlet and triplet structures of interest were investigated by using high‐level theoretical methods with correlation‐consistent basis sets up to pentuple ζ. The coupled cluster methods adopted included up to full triple excitations and perturbative quadruples. In contrast to earlier studies that predicted the twisted C_2v triplet to be the ground state, we found a peculiar planar C_s singlet ground state in the present research. The lowest excited electronic state of 1,1‐dilithioethylene, the twisted C_s triplet, was found to lie 9.0 kcal mol^?1 above the ground state by using energy extrapolation to the complete basis set limit. For the planar C_s singlet and twisted C_s triplet states of 1,1‐dilithioethylene, anharmonic vibrational frequencies were reported on the basis of second‐order vibrational perturbation theory. The remarkably low (2050 cm^?1) C?H stretching fundamental (the C?H bond near the bridging lithium) of the singlet state was found to have very strong infrared intensity. These highly reliable theoretical findings may assist in the long‐sought experimental identification of 1,1‐dilithioethylene. Using natural bond orbital analysis, we found that lithium bridging structures were strongly influenced by electrostatic effects. All carbon–carbon linkages corresponded to conventional double bonds.     

C-Br Bond Dissociation Mechanisms of 2-Bromothiophene and 3-Bromothiophene at 267 nm

C-Br bond dissociation mechanisms of 2-bromothiophene and 3-bromothiophene at 267 nm were investigated using ion velocity imaging technique. Translational energy distributions and angular distributions of the photoproducts, Br(²P_3/2) and Br^*(²P_½), were obtained and the possible dissociation channels were analyzed. For these two bromothiophenes, the Br fragments were produced via three channels: (i) the fast predissociation following the intersystem crossing from the excited singlet state to repulsive triplet state; (ii) the hot dissociation on highly vibrational ground state following the internal conversion of the excited singlet state; and (iii) the dissociation following the multiphoton ionization of the parent molecules. Similar channels are involved for photoproduct Br^* of the 2-bromothiophene dissociation at 267 nm; whereas for the photoproduct Br^* of 3-bromothiophene, the dissociation channel via internal conversion from the excited singlet state to highly vibrational ground state became dominating and the fast predissociation channel via the excited triplet state almost disappeared. Informations about the relative contribution, energy disposal, and the anisotropy of each channel were quantitatively given. It was found that with the position of Br atom in thienyl being far from S atom, the relative ratios of products from channels (i) and (ii) decreased obviously and the anisotropies corresponding to each channel became weaker.     

Intramolecular photoexcitation dynamics and magnetic field effects in an intermediate-case molecule

Molecular vibration and rotation play a significant role in the intramolecular photoexcitation dynamics of the so-called intermediate-case molecule, and the fluorescence intensity, decay and polarization of s-triazine vapor are shown to depend on the excited rovibronic level of the S₁ state. Fluorescence characteristics are interpreted by assuming three zero-order states: (1) a zero-order singlet state that carries the absorption intensity and emits fluorescence with sharp structure; (2) zero-order singlet states that do not carry the absorption intensity but emit broad fluorescence; and (3) zero-order triplet states. The interaction among these states depends not only on the vibrational level but also on the rotational level excited. It is suggested that the number of triplet states coupled to the singlet state increases with increasing excess vibrational energy. It is also suggested that K-scrambling occurs both in the triplet manifold following intersystem crossing (ISC) and in the singlet manifold following intramolecular vibrational energy redistribution (IVR). The fluorescence intensity and decay of s-triazine vapor are significantly influenced by a magnetic field, and the field effects are interpreted in terms of the spin decoupling in the triplet manifold following ISC; the role of external magnetic fields is to mix the spin sublevels of different rovibronic levels coupled to the excited singlet state. Magnetic depolarization of fluorescence also occurs because of the efficient interaction between the excited singlet state and the triplet state.     

Transient Raman studies of the cis—trans photoisomerization processes in stilbene and retinal

This article reviews the present status of the application of transient or time-resolved Raman spectroscopy to the mechanistic studies of the cis—trans photoisomerization in conjugated molecules. Attention is focused on the vibrational information about the molecular structure of the electronically excited intermediates which are involved in the process of photoisomerization. Two examples, the trans to cis photoisomerization of stilbene through the lower excited singlet state and the cist to trans isomerization of retinal through the lowest excited triplet state, are included.     

Electronic and Vibrational Coherence Dynamics in a Cyanine Dye Studied Using a Few‐Cycle Pulsed Laser

We report the relaxation times of electronic and vibrational coherence in the cyanine dye 1,1′,3,3,3′,3′‐hexamethyl‐4,4′,5,5′‐dibenzo‐2,2′‐indotricarbocyanine, measured using a 7.1 fs pulsed laser. The vibrational phase relaxation times are found to be between 380 and 680 fs in the ground and lowest excited singlet states. The vibrational dephasing times of the 294, 446, and 736 cm^?1 modes are relatively long among the six modes associated with excited‐state wave packets. The slower relaxations are explained in terms of a coupled triplet of vibrational modes, which preserves coherence by forming a tightly bound group to satisfy the condition of circa conservation of vibrational energy. Using data from the negative‐time range (i.e., when the probe pulse precedes the pump pulse), the electronic phase relaxation time is found to be 31±1 fs. The dynamic vibrational mode in the excited state (1171 cm^?1), detected in the positive‐time range, is also studied from the negative‐time traces under the same experimental conditions.     

Quantum chemical calculations of electronically excited states: formamide, its protonated form and alkali cation complexes as case studies

The properties of formamide, its protonated form and interaction complexes with lithium and sodium cations were studied in electronically excited singlet states by means of high-level multireference ab initio methods. The vertical excitation energies show a marked influence on protonation with particular large effects found for the O-protonated form as compared to neutral formamide. Complexation with Li⁺ and Na⁺ leads to a pronounced shift of the n_O–π^* state to higher energies while the π–π^* state moves in opposite direction. Geometry optimizations in the lowest excited singlet show strong geometrical effects leading to pyramidalization at the N and C atoms. The photodynamical simulations performed for formamide in the first excited singlet state show that the main primary deactivation path is CN dissociation with a lifetime of about 420?fs.     

Excited States of Weak Interacting Complexes of Formaldehyde and Alkali Metal Ions

The electronically excited states of formaldehyde and its complexes with alkali metal ions are investigated with the time-dependent density functional theory (TD DFT) method. Vertical transition energies for several singlet and triplet excited states, adiabatic transition energies for the first singlet and triplet excited states S₁ and T₁, the adiabatic geometries and vibrational frequencies of the ground state S₀ and the first singlet and triplet excited states S₁ and T₁ for formaldehyde and its complexes are calculated. Better agreement with the experiment than that of the CIS method is obtained for CH₂O at the TD DFT level. The nonlinear C=O?M⁺ interaction in the excited states S₁ and T₁ is weaker than the linear interaction in the ground state. In the S₀ and S₁ states, the C=O bond is elongated by cation complexation and its stretching frequency is red-shifted, but in the T₁ state the C=O bond is shortened and its frequency is blue-shifted.     

Time‐dependent density functional theory study on the electronic excited‐state hydrogen‐bonding dynamics of 4‐aminophthalimide (4AP) in aqueous solution: 4AP and 4AP–(H2O)1,2 clusters

The time‐dependent density functional theory (TDDFT) method has been carried out to investigate the excited‐state hydrogen‐bonding dynamics of 4‐aminophthalimide (4AP) in hydrogen‐donating water solvent. The infrared spectra of the hydrogen‐bonded solute?solvent complexes in electronically excited state have been calculated using the TDDFT method. We have demonstrated that the intermolecular hydrogen bond C? O···H? O and N? H···O? H in the hydrogen‐bonded 4AP?(H₂O)₂ trimer are significantly strengthened in the electronically excited state by theoretically monitoring the changes of the bond lengths of hydrogen bonds and hydrogen‐bonding groups in different electronic states. The hydrogen bonds strengthening in the electronically excited state are confirmed because the calculated stretching vibrational modes of the hydrogen bonding C?O, amino N? H, and H? O groups are markedly red‐shifted upon photoexcitation. The calculated results are consistent with the mechanism of the hydrogen bond strengthening in the electronically excited state, while contrast with mechanism of hydrogen bond cleavage. Furthermore, we believe that the transient hydrogen bond strengthening behavior in electroniclly excited state of chromophores in hydrogen‐donating solvents exists in many other systems in solution. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Spectroscopic Properties of 4‐Pyridoxic Acid as a Function of pH and Solvent

The photophysical properties and acid/base equilibria of 4‐pyridoxic acid (=3‐hydroxy‐5‐(hydroxymethyl)‐2‐methylpyridine‐4‐carboxylic acid), the final product of the catabolism of vitamin B₆, have been studied in aqueous solutions. The ground state of 4‐pyridoxic acid exhibits the different protonated forms A – D in the range of H₀=?6 to pH 11.5. HMQC‐ and HMBC‐NMR Studies allowed the pH‐dependent assignment of the different C‐atoms, and the evaluation of the deprotonation sequence. The 3‐OH group in the ground state has a ‘pK_a’ of H₀=?0.64, which is much lower than that found for other vitamin B₆ related compounds. The pK_a value of the 4‐COOH group is 5.4. Fluorescence studies showed that the same species exist at the lowest excited singlet state, but in different pH ranges. The 3‐OH group is four pH units more acidic in the lowest excited singlet state than in the ground state. Excitation spectra and emission decays in the pH range of 8 to 11.5 indicate that the pyridine N‐atom is more basic in the excited singlet state than in the ground state. The emission spectra are red‐shifted in protic solvents, in agreement with an intramolecular H‐bond between the ionized 3‐OH group and the nonionized 4‐COOH group.     

Fluorescence from subpicosecond states of 3,4,9,10-dibenzpyrene

A systematic study has been made of the fluorescence from higher excited singlet states of 3,4,9,10-dibenzpyrene. Particular attention has been paid to the dependence on the excitation conditions of the intensity, structure and overall shape of the fluorescence spectra. It is confirmed that the upper states relax electronically before significant vibrational relaxation occurs: in fact excess vibrational energy is found to increase the rate of internal conversion, consistently with observations made on isolated small molecules. Calculations have been made of the relaxation times of several electronic states, all in the subpicosecond region.     

Ultrafast Relaxation Dynamics of the Excited States of 1‐Amino‐ and 1‐(N,N‐Dimethylamino)‐fluoren‐9‐ones

The dynamics of the excited states of 1‐aminofluoren‐9‐one (1AF) and 1‐(N,N‐dimethylamino)‐fluoren‐9‐one (1DMAF) are investigated by using steady‐state absorption and fluorescence as well as subpicosecond time‐resolved absorption spectroscopic techniques. Following photoexcitation of 1AF, which exists in the intramolecular hydrogen‐bonded form in aprotic solvents, the excited‐state intramolecular proton‐transfer reaction is the only relaxation process observed in the excited singlet (S₁) state. However, in protic solvents, the intramolecular hydrogen bond is disrupted in the excited state and an intermolecular hydrogen bond is formed with the solvent leading to reorganization of the hydrogen‐bond network structure of the solvent. The latter takes place in the timescale of the process of solvation dynamics. In the case of 1DMAF, the main relaxation pathway for the locally excited singlet, S₁(LE), or S₁(ICT) state is the configurational relaxation, via nearly barrierless twisting of the dimethylamino group to form the twisted intramolecular charge‐transfer, S₁(TICT), state. A crossing between the excited‐state and ground‐state potential energy curves is responsible for the fast, radiationless deactivation and nonemissive character of the S₁(TICT) state in polar solvents, both aprotic and protic. However, in viscous but strong hydrogen‐bond‐donating solvents, such as ethylene glycol and glycerol, crossing between the potential energy surfaces for the ground electronic state and the hydrogen‐bonded complex formed between the S₁(TICT) state and the solvent is possibly avoided and the hydrogen‐bonded complex is weakly emissive.     

Singlet and Triplet Excited States and Intersystem Crossing in Free‐Base Porphyrin: TDDFT and DFT/MRCI Study

Extensive time-dependent DFT (TDDFT) and DFT/multireference configuration interaction (MRCI) calculations are performed on the singlet and triplet excited states of free-base porphyrin, with emphasis on intersystem crossing processes. The equilibrium geometries, as well as the vertical and adiabatic excitation energies of the lowest singlet and triplet excited states are determined. Single and double proton-transfer reactions in the first excited singlet state are explored. Harmonic vibrational frequencies are calculated at the equilibrium geometries of the ground state and of the lowest singlet and triplet excited states. Furthermore, spin–orbit coupling matrix elements of the lowest singlet and triplet states and their numerical derivatives with respect to nuclear displacements are computed. It is shown that opening of an unprotonated pyrrole ring as well as excited-state single and double proton transfer inside the porphyrin cavity lead to crossings of the potential energy curves of the lowest singlet and triplet excited states. It is also found that displacements along out-of-plane normal modes of the first excited singlet state cause a significant increase of the 2|H_so|S₁>, 1|H_so|S₁>, and 1|H_so|S₀> spin–orbit coupling matrix elements. These phenomena lead to efficient radiationless deactivation of the lowest excited states of free-base porphyrin via intercombination conversion. In particular, the S₁→T₁ population transfer is found to proceed at a rate of ≈10⁷ s⁻¹ in the isolated molecule.     

Energy transfer processes involving ultraviolet stabilizers. Quenching of singlet oxygen

The role of electronically excited singlet (¹Δ_g) oxygen molecules in the photooxidation of polymers has received increased attention in recent years. Little information regarding the interaction of ultraviolet stabilizers with singlet oxygen is known, however. In this study, singlet oxygen was produced by a microwave discharge in a flow system and rate constants were obtained for quenching by ultraviolet stabilizers. It was found that some nickel chelate stabilizers are effective quenchers of singlet oxygen and their quenching behaviors can be correlated with ultraviolet stabilization effectiveness in thin polypropylene and polyethylene films. The best oxygen quenchers of those examined are nickel chelates with sulfur donor ligands.     

Photophysics of Schiff Bases: Theoretical Study of Salicylidene Methylamine

The proton‐transfer reaction in a model aromatic Schiff base, salicylidene methylamine (SMA), in the ground and in the lowest electronically‐excited singlet states, is theoretically analyzed with the aid of second‐order approximate coupled‐cluster model CC2, time‐dependent density functional theory (TD‐DFT) using the Becke, three‐parameter Lee–Yang–Parr (B3LYP) functional, and complete active space perturbation theory CASPT2 electronic structure methods. Computed vertical‐absorption spectra for the stable ground‐state isomers of SMA fully confirm the photochromism of SMA. The potential‐energy profiles of the ground and the lowest excited singlet state are calculated and four photophysically relevant isomeric forms of SMA; α, β, γ, and δ are discussed. The calculations indicate two S₁/S₀ conical intersections which provide non‐adiabatic gates for a radiationless decay to the ground state. The photophysical scheme which emerges from the theoretical study is related to recent experimental results obtained for SMA and its derivatives in the low‐temperature argon matrices (J. Grzegorzek, A. Filarowski, Z. Mielke, Phys. Chem. Chem. Phys. 2011 , 13, 16596–16605). Our results suggest that aromatic Schiff bases are potential candidates for optically driven molecular switches.     

Synthesis,Structural Characterization,Photophysics, and Broadband Nonlinear Absorption of a Platinum(II) Complex with the 6‐(7‐Benzothiazol‐2′‐yl‐9,9‐diethyl‐9 H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl Ligand

A platinum complex with the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl ligand ( 1 ) was synthesized and the crystal structure was determined. UV/Vis absorption, emission, and transient difference absorption of 1 were systematically investigated. DFT calculations were carried out on 1 to characterize the electronic ground state and aid in the understanding of the nature of low‐lying excited electronic states. Complex 1 exhibits intense structured ¹π–π* absorption at λ_abs<440 nm, and a broad, moderate ¹M LCT/¹LLCT transition at 440–520 nm in CH₂Cl₂ solution. A structured ³π–π*/³M LCT emission at about 590 nm was observed at room temperature and at 77 K. Complex 1 exhibits both singlet and triplet excited‐state absorption from 450 nm to 750 nm, which are tentatively attributed to the ¹π–π* and ³π–π* excited states of the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridine ligand, respectively. Z‐scan experiments were conducted by using ns and ps pulses at 532 nm, and ps pulses at a variety of visible and near‐IR wavelengths. The experimental data were fitted by a five‐level model by using the excited‐state parameters obtained from the photophysical study to deduce the effective singlet and triplet excited‐state absorption cross sections in the visible spectral region and the effective two‐photon absorption cross sections in the near‐IR region. Our results demonstrate that 1 possesses large ratios of excited‐state absorption cross sections relative to that of the ground‐state in the visible spectral region; this results in a remarkable degree of reverse saturable absorption from 1 in CH₂Cl₂ solution illuminated by ns laser pulses at 532 nm. The two‐photon absorption cross sections in the near‐IR region for 1 are among the largest values reported for platinum complexes. Therefore, 1 is an excellent, broadband, nonlinear absorbing material that exhibits strong reverse saturable absorption in the visible spectral region and large two‐photon‐assisted excited‐state absorption in the near‐IR region.