Following evolution of bacteriorhodopsin in its reactive excited state via stimulated emission pumping

New information concerning the photochemical dynamics of bacteriorhodopsin (BR) is obtained by impulsively stimulating emission from the reactive fluorescent state. Depletion of the excited-state fluorescence leads to an equal reduction in production of later photoproducts. Accordingly, chromophores which are forced back to the ground state via emission do not continue on in the photocycle, conclusively demonstrating that the fluorescent state is a photocycle intermediate. The insensitivity of depletion dynamics to the "dump" pulse timing, throughout the fluorescent states lifetime, and the biological inactivity of the dumped population suggest that the fluorescent-state structure is constant, well-defined, and significantly different than that where crossing to the ground state takes place naturally. In conjunction with conclusions from comparing the photophysics of BR with those of synthetic analogues containing "locked" retinals, present results show that large-amplitude torsion around C13=C14 is required to go between the above structures.     

Ab initio study of the formation of bis-heterocyclic compound involving Si and Ge from dichlorosilylene germylidene (Cl2Si=Ge:) and ethene

The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene (Cl₂Si=Ge:) and ethene has been investigated with CCSD(T)//MP2/6-31G* method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Due to the sp ³ hybridization of the Ge: atom in Si-heterocyclic four-membered ring germylene, the Si-heterocyclic four-membered ring germylene further combined with the ethene to form a bis-heterocyclic compound with Si and Ge.     

Fluorescence of ammonia-d3 from its first excited singlet state

Structured emission spectra have been observed from ND₃ excited at 2139 Å and 2144 Å. The emission is short-lived (τ_{$\text{1}\text{2}$} < 10^?10 s) and has been assigned to the ND₃($\text{A}$) → ND₃($\text{X}$) fluorescence transition.     

Ab initio study of mechanism of forming bis-heterocyclic compound with Si and Ge between dimethylsilylene germylidene (Me2Si=Ge:) and ethene

The mechanism of the cycloaddition reaction between singlet dimethylsilylene germylidene (Me₂Si=Ge:) and ethene has been investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rules presented is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Due to the sp ³ hybridization of the Ge: atom in Si-heterocyclic four-membered ring germylene, the Si-heterocyclic four-membered ring germylene further combined with ethene to form a bis-heterocyclic product with Si and Ge (P2).     

Relaxation dynamics of the first excited electronic singlet state of azulene in solution

An upper limit to the relaxation time of the first excited electronic singlet state (S₁) of azulene in cyclohexane has been determined for two excitation frequencies. The lifetimes of S₁ excited by single picosecond duration optical pulses of frequency 18910 cm^?1 and 16000 cm^?1 are ? 1 ps and ? 2 ps respectively.     

Second excited singlet state emission spectroscopy of thiocarbonyls. I. Thiophosgene

Well resolved emission spectra have been recorded after dye laser excitation of low-lying vibronic levels in the $\text{B}$(¹A₁) state of Cl₂CS. The effects of substrate pressure, added SF₆ and excitation wavelength on the spectra are reported. A Franck-Condon analysis suggests that the excited state CS bond length is 0.5 Å longer than in the ground state.     

Fast hydrogen elimination from the [Ru(PH3)3(CO)(H)2] complex in the first singlet excited states. A quantum dynamics study

The photodissociation dynamics of [Ru(PH₃)₃(CO)(H)₂] complex in the lowest two singlet excited electronic states has been theoretically analyzed. Reduced two-dimensional potential energy surfaces (PES) are built up by combining a time-dependent method to calculate the excited states energy with DFT (B3LYP) electronic calculations of the ground state. By means of a Fast Fourier Transform (FFT) algorithm the time evolution of the wavefunction upon vertical transition from the minimum of the ground state to both diabatic states has been followed. The propagation in S₁, the lowest in energy at the vertical transition point and the one with a larger transition probability from the ground state, discloses that the system is not evolving from the initial position at least in the time spanned by the calculations. Conversely the H₂ elimination is very fast (about 37 fs) in the S₂ state. In this state the vertical transition puts the system in a purely dissociative zone of the PES. In that state FFT results indicate that the lengthening of the Ru–H₂ distance and the shortening of the H–H one are taking place almost simultaneously.     

A generalization of the method of stimulated emission pumping

Drawing on the results of an analysis of the nature of the pulse that generates complete transfer of population from one to another level in a system with a discrete spectrum, a generalization of the method of stimulated emission pumping is proposed. It is shown that a small subset of the Fourier components of the optimal pulse will, if their relative amplitudes are the same as in the optimal pulse, generate almost as efficient a population transfer, thereby generating the opportunity to prepare a system in a selected state with a selected population.     

A blue digermene (t-Bu2MeSi)2Ge=Ge(SiMet-Bu2)2

A novel tetrakis(trialkylsilyl)digermene, featuring rather unusual structural and chemical properties, was synthesized by a straightforward synthetic protocol: reduction of the corresponding dichlorobis(trialkylsilyl)germane precursor with potassium graphite.     

Photon induced isomerization in the first excited state of the 7-azaindole-(H2O)3 cluster

A picosecond pump and probe experiment has been applied to study the excited state dynamics of 7-azaindole-water 1?∶?2 and 1?∶?3 clusters [7AI(H(2)O)(2,3)] in the gas phase. The vibrational-mode selective Excited-State-Triple-Proton Transfer (ESTPT) in 7AI(H(2)O)(2) proposed from the frequency-resolved study has been confirmed by picosecond decays. The decay times for the vibronic states involving the ESTPT promoting mode σ(1) (850-1000 ps) are much shorter than those for the other vibronic states (2100-4600 ps). In the (1 + 1) REMPI spectrum of 7AI(H(2)O)(3) measured by nanosecond laser pulses, the vibronic bands with an energy higher than 200 cm(-1) above the origin of the S(1) state become very weak. In contrast, the vibronic bands in the same region emerge in the (1 + 1') REMPI spectrum of 7AI(H(2)O)(3) with picosecond pulses. The decay times drastically decrease when increasing the vibrational energy above 200 cm(-1). Ab initio calculations show that a second stable "cyclic-nonplanar isomer" exists in addition to a "bridged-planar isomer", and that an isomerization from a bridged-planar isomer to a cyclic-nonplanar isomer is most probably responsible for the short lifetimes of the vibronic states of 7AI(H(2)O)(3).     

Ground and low-lying excited states of propadienylidene (H2C=C=C:) obtained by negative ion photoelectron spectroscopy

A joint experimental-theoretical study has been carried out on electronic states of propadienylidene (H(2)CCC), using results from negative-ion photoelectron spectroscopy. In addition to the previously characterized X(1)A(1) electronic state, spectroscopic features are observed that belong to five additional states: the low-lying ?(3)B(1) and b(3)A(2) states, as well as two excited singlets, ?(1)A(2) and B(1)B(1), and a higher-lying triplet, c(3)A(1). Term energies (T(0), in cm(-1)) for the excited states obtained from the data are: 10,354±11 (?(3)B(1)); 11,950±30 (b(3)A(2)); 20,943±11 (c(3)A(1)); and 13,677±11 (?(1)A(2)). Strong vibronic coupling affects the ?(1)A(2) and B(1)B(1) states as well as ?(3)B(1) and b(3)A(2) and has profound effects on the spectrum. As a result, only a weak, broadened band is observed in the energy region where the origin of the B(1)B(1) state is expected. The assignments here are supported by high-level coupled-cluster calculations and spectral simulations based on a vibronic coupling Hamiltonian. A result of astrophysical interest is that the present study supports the idea that a broad absorption band found at 5450 ? by cavity ringdown spectroscopy (and coincident with a diffuse interstellar band) is carried by the B(1)B(1) state of H(2)CCC.     

Second excited singlet state emission spectroscopy of thiocarbonyls. II. Thiocarbonyl chlorofluoride

Single vibronic level emission spectra have been measured for four excitation wavelengths pumping the second excited singlet state of CIFCS. Only resonance fluorescence is observed. Progressions involving Δv″₁ = 0, 1, 2, …, Δv″₆ = 0, 2, 4 … dominate. Analysis of the spectra indicates that neither intra- or intermolecular processes lead to odd Δv′₆ changes and that collisions in the pure gas lead to electronic quenching of molecules in the excited state.     

Incomplete vibrational relaxation of pyrene in its first excited singlet state in the vapour phase

The non-exponential fluorescence decay of pyrene is assigned to incomplete vibrational relaxation in the first excited singlet state. The increasing rate of this fluorescence decay with increasing vibrational energy is mainly attributed to an increase of the intersystem-crossing rate and to a smaller extent to a temperature dependence of the radiative rate constant.     

Phototautomerism in the lowest excited singlet state of 1-hydroxy-2-carboxyanthraquinone

The dependence of the absorption and fluorescence spectra of 1-hydroxy-2-carboxy-anthraquinone on pH and Hammett acidity have been studied. This compound exhibits phototautomerism in its uncharged and its singly-charged anionic species in aqueous media. Its ground state (pK(a)) and lowest excited singlet-state (pK(a)( *)) dissociation constants have been determined by absorptiometric and fluorimetric titrations and the assignment of the pK(a) and pK( *)(a) values to the equilibria concerned has been carefully considered.     

A theoretical study of the ground and first excited singlet state proton transfer reaction in isolated 7-azaindole–water complexes

A systematic study of the proton transfer in the 7-azaindole–water clusters (7-AI(H₂O)_n; n=1–4) in both the ground and first excited singlet electronic states is undertaken. DFT(B3LYP) calculations for the ground electronic state shows that the more stable geometry of the initial normal tautomer presents a cyclic set of hydrogen bonds that links the two nitrogen atoms of the base across the waters. For the n=4 cluster the water molecules adopt a double ring structure so that two cycles of hydrogen bonds are found there. From this structure full tautomerization implies only one transition state so that a concerted but non-synchronous process is predicted by our theoretical calculations. This behavior is found both in the ground and the excited states where CIS geometry optimizations and TD(B3LYP) energy calculations are performed. The difference between both states is the height of the energy barrier that is much lower in the excited state. Another clear difference between both electronic states is that full tautomerization is an endergonic process in the ground state whereas it is clearly exergonic (then favorable) in the excited state. This is so because electronic excitation implies a charge transfer from the five-member cycle to the six-member one of 7-azaindole so that the proton transfer from the pyrrolic side to the pyridinic one is favored. These results clearly indicate that full tautomerization will not likely occur in the ground state but it will be quite easy (and fast) in the excited state. Reaction is already feasible in the S₁ 1:1 complex but it is faster in the 1:2 complex. However the reaction slows again for the 1:3 complex and, finally, reaches a new maximum for the largest cluster studied here, the n=4 case. These results, which are in agreement with experimental data, are explained in terms of the number of hydrogen bonds that are involved in the transfer. The proton transfer through a ring formed by the substrate and two water molecules is found to be the more efficient one, at least in this system.     

Theoretical study on the singlet excited state of pterin and its deactivation pathway

The excited-state properties and related photophysical processes of the acidic and basic forms of pterin have been investigated by the density functional theory and ab initio methodologies. The solvent effects on the low-lying states have been estimated by the polarized continuum model and combined QM/MM calculations. Calculations reveal that the observed two strong absorptions arise from the strong pi --> pi* transitions to 1(pipi*L(a)) and 1(pipi*L(b)) in the acidic and basic forms of pterin. The first 1(pipi*L(a)) excited state is exclusively responsible for the experimental emission band. The vertical 1(n(N)pi*) state with a small oscillator strength, slightly higher in energy than the 1(pipi*L(a)) state, is less accessible by the direct electronic transition. The 1(n(N)pi*) state may be involved in the photophysical process of the excited pterin via the 1(pipi*L(a)/n(N)pi*) conical intersection. The radiationless decay of the excited PT to the ground state experiences a barrier of 13.8 kcal/mol for the acidic form to reach the (S(1)/S(0)) conical intersection. Such internal conversion can be enhanced with the increase in excitation energy, which will reduce the fluorescence intensity as observed experimentally.