堆积的腺嘌呤体系新失活通道的动力学模拟

采用半经典动力学方法模拟了激光诱导下π堆积的腺嘌呤体系最低激发态的失活过程. 模拟激光脉冲仅作用于一个腺嘌呤分子. 发现随着激发态腺嘌呤分子(A)与基态腺嘌呤分子(A′)之间距离的缩短, 它们的相互作用显著增强. 分子间的相互作用导致了一条新的失活通道, 即C₂原子与C₂′原子靠拢成键, 形成“成键的激基复合体”的中间体. 中间体的寿命约为390 fs. C₂原子的畸变和H₂′原子的环面外振动导致中间体失活. 失活后C₂－C₂′断裂, 释放的键能转化为分子动能, 腺嘌呤分子恢复基态的平面结构.     

堆积的胸腺嘧啶体系光物理失活的动力学模拟

采用半经典动力学方法模拟了π堆积的胸腺嘧啶体系最低激发态的光物理失活过程.设置激光脉冲仅作用于一个胸腺嘧啶分子T,另一胸腺嘧啶分子T’保持基态.模拟发现由于T与T’之间存在π堆积相互作用,导致电荷转移,形成T带负电荷、T’带正电符的激基复合物.由于相邻分子的空间效应阻碍了激发的T分子到达圆锥相交所必需的强烈扭曲,激基复合物的寿命比单体增长.当分子间距离缩短至0.3 nm后,T分子C₅—C₆键扭曲程度最大,此时发生电荷重组,两个胸腺嘧啶分子均恢复电中性.电荷重组诱导T’分子发生畸变,并在C₅’—C₆’扭曲最大时避免相交,体系衰减至基态,T和T’分子均恢复平面构型.     

Femtosecond time- and wavelength-resolved fluorescence and absorption spectroscopic study of the excited states of adenosine and an adenine oligomer

By employing broadband femtosecond Kerr-gated time-resolved fluorescence (KTRF) and transient absorption (TA) techniques, we report the first (to our knowledge) femtosecond combined time- and wavelength-resolved study on an ultraviolet-excited nucleoside and a single-stranded oligonucleotide (namely adenosine (Ado) and single-stranded adenine oligomer (dA)(20)) in aqueous solution. With the advantages of the ultrafast time resolution, the broad spectral and temporal probe window, and a high sensitivity, our KTRF and TA results enable the real time monitoring and spectral characterization of the excited-state relaxation processes of the Ado nucleoside and (dA)(20) oligonucleotide investigated. The temporal evolution of the 267 nm excited Ado KTRF spectra indicates there are two emitting components with lifetimes of approximately 0.13 ps and approximately 0.45 ps associated with the L(a) and L(b) pipi* excited states, respectively. These Ado results reveal no obvious evidence for the involvement of the npi* state along the irradiative internal conversion pathway. A distinct mechanism involving only the two pipi* states has been proposed for the ultrafast Ado deactivation dynamics in aqueous solution. The time dependence of the 267 nm excited (dA)(20) KTRF and TA spectra reveals temporal evolution from an ultrafast "A-like" state (with a approximately 0.39 ps decay time) to a relatively long-lived E(1) "excimer" (approximately 4.3 ps decay time) and an E(2) "excimer-like" (approximately 182 ps decay time) state. The "A-like" state has a spectral character closely resembling the excited state of Ado. Comparison of the spectral evolution between the results for Ado and (dA)(20) provides unequivocal evidence for the local excitation character of the initially photoexcited (dA)(20). The rapid transformation of the locally excited (dA)(20) component into the delocalized E(1) "excimer" state which then further evolves into the E(2) "excimer-like" state indicates that base stacking has a high ability to modify the excited-state deactivation pathway. This modification appears to occur by suppressing the internal conversion pathway of an individually excited base component where the stacking interaction mediates efficient interbase energy transfer and promotes formation of the collective excited states. This feature of the local excitation that is subsequently followed by rapid energy delocalization into nearby bases may occur in many base multimer systems. Our results provide an important new contribution to better understanding DNA photophysics.     

π堆积的腺嘌呤-胸腺嘧啶体系激发态电荷转移和无辐射失活的半经典动力学模拟

采用半经典电子-辐射-离子动力学(SERID)模型模拟了π堆积的腺嘌呤-胸腺嘧啶(A-T)体系激发态的光物理失活过程. 设置激光脉冲仅作用于T, 模拟发现电子由A转移到T, 形成(A⁺T^-)^*激基缔合物(exciplex). 当分子间距缩短至0.300 nm时, 由于轨道离域效应产生电荷重组, 体系恢复电中性; 当A分子的C4'－C5'扭曲程度最大时, 体系通过避免交叉点衰减至基态. Exciplex 的失活途径由分子间距离和A分子的变形程序两个因素决定. 由于A分子的C4'、C5'原子位阻较大, 难以达到失活所必需的强烈扭曲, 因此(A-T)^*的寿命比胸腺嘧啶堆积体系(T-T)^*显著增长.     

Ultrafast excited-state dynamics of adenine and monomethylated adenines in solution: implications for the nonradiative decay mechanism

The DNA base adenine and four monomethylated adenines were studied in solution at room temperature by femtosecond pump-probe spectroscopy. Transient absorption at visible probe wavelengths was used to directly observe relaxation of the lowest excited singlet state (S(1) state) populated by a UV pump pulse. In H(2)O, transient absorption signals from adenine decay biexponentially with lifetimes of 0.18 +/- 0.03 ps and 8.8 +/- 1.2 ps. In contrast, signals from monomethylated adenines decay monoexponentially. The S(1) lifetimes of 1-, 3-, and 9-methyladenine are similar to one another and are all below 300 fs, while 7-methyladenine has a significantly longer lifetime (tau = 4.23 +/- 0.13 ps). On this basis, the biexponential signal of adenine is assigned to an equilibrium mixture of the 7H- and 9H-amino tautomers. Excited-state absorption (ESA) by 9-methyladenine is 50% stronger than by 7-methyladenine. Assuming that ESA by the corresponding tautomers of adenine is unchanged, we estimate the population of 7H-adenine in H(2)O at room temperature to be 22 +/- 4% (estimated standard deviation). To understand how the environment affects nonradiative decay, we performed the first solvent-dependent study of nucleobase dynamics on the ultrafast time scale. In acetonitrile, both lowest energy tautomers of adenine are present in roughly similar proportions as in water. The lifetimes of the 9-substituted adenines depend somewhat more sensitively on the solvent than those of the 7-substituted adenines. Transient signals for adenine in H(2)O and D(2)O are identical. These solvent effects strongly suggest that excited-state tautomerization is not an important nonradiative decay pathway. Instead, the data are most consistent with electronic energy relaxation due to state crossings between the optically prepared (1)pipi* state and one or more (1)npi* states and the electronic ground state. The pattern of lifetimes measured for the monomethylated adenines suggests a special role for the (1)npi* state associated with the N7 electron lone pair.     

Detailed dynamics of the nonradiative deactivation of adenine: a semiclassical dynamics study

A realistic dynamics simulation study is reported for the ultrafast radiationless deactivation of 9H-adenine. The simulation follows two different excitations induced by two 80 fs (fwhm) laser pulses that are different in energy: one has a photon energy of 5.0 eV, and the other has a photon energy of 4.8 eV. The simulation shows that the excited molecule decays to the electronic ground state from the (1)pipi* state in both excitations but through two different radiationless pathways: in the 5.0 eV excitation, the decay channel involves the out-of-plane vibration of the amino group, whereas in the 4.8 eV excitation, the decay strongly associates with the deformation of the pyrimidine at the C 2 atom. The lifetime of the (1) npi* state determined in the simulation study is 630 fs for the 5.0 eV excitation and 1120 fs for the 4.8 eV excitation. These are consistent with the experimental values of 750 and 1000 fs. We conclude that the experimentally observed difference in the lifetime of the (1) npi* state at various excitations results from the different radiationless deactivation pathways of the excited molecule to the electronic ground state.     

A three-state model for the photophysics of adenine

An ab initio theoretical study at the CASPT2 level is reported on minimum energy reaction paths, state minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of two tautomers of adenine: 9H- and 7H-adenine. The obtained results led to a complete interpretation of the photophysics of adenine and derivatives, both under jet-cooled conditions and in solution, within a three-state model. The ultrafast subpicosecond fluorescence decay measured in adenine is attributed to the low-lying conical intersection (gs/pipi* La)(CI), reached from the initially populated 1(pipi* La) state along a path which is found to be barrierless only in 9H-adenine, while for the 7H tautomer the presence of an intermediate plateau corresponding to an NH2-twisted conformation may explain the absence of ultrafast decay in 7-substituted compounds. A secondary picosecond decay is assigned to a path involving switches towards two other states, 1(pipi* Lb) and 1(npi*), ultimately leading to another conical intersection with the ground state, (gs/npi*), with a perpendicular disposition of the amino group. The topology of the hypersurfaces and the state properties explain the absence of secondary decay in 9-substituted adenines in water in terms of the higher position of the 1(npi*) state and also that the 1(pipi* Lb) state of 7H-adenine is responsible for the observed fluorescence in water. A detailed discussion comparing recent experimental and theoretical findings is given. As for other nucleobases, the predominant role of a pipi*-type state in the ultrafast deactivation of adenine is confirmed.     

Detailed mechanism for photoinduced cytosine dimerization: a semiclassical dynamics simulation

Semiclassical dynamics simulation is used to study dimerization of two stacked cytosine molecules following excitation by ultrashort laser pulses (25 fs fwhm, Gaussian, 4.1 eV photon energy). The initial excited state was found to form an ultrashort exciton state, which eventually leads to the formation of an excimer state by charge transfer. When the interbase distance, defined as an average value of C(5)-C(5)' and C(6)-C(6)', becomes less than 3 ?, charge recombination occurs due to strong intermolecular interaction, eventually leading to an avoided crossing within 20-30 fs. Geometries at the avoided crossing, with average intermolecular distance of about 2.1 ?, are in accord with CASSCF/CASPT2 calculations. Results indicate that the C(2)-N(1)-C(6)-C(5) and C(2)'-N(1)'-C(6)'-C(5)' dihedral angles' bending vibrations play a significant role in the vibronic coupling between the HOMO and LUMO, which leads to a nonadiabatic transition to the electronic ground state.     

Femtosecond dynamics of isolated phenylcarbenes

Understanding the primary photophysical processes in molecules is essential for interpreting their photochemistry, because molecules rarely react from the initially excited electronic state. In this study the ultrafast excited-state dynamics of chlorophenylcarbene (CPC) and trifluoromethylphenylcarbene (TFPC), two species that are considered as models for carbene dynamics, were investigated by femtosecond time-resolved pump probe spectroscopy in the gas phase. Their dynamics was followed in real time by time-resolved photoionization and photoelectron imaging. CPC was excited at 265 nm into the 3 1A' state, corresponding to excitation from a pi-orbital of the aromatic ring into the LUMO. The LUMO contains a contribution of the p-orbital at the carbene center. Three time constants are apparent in the photoelectron images: A fast decay process with tau1 approximately 40 fs, a second time constant of tau2 approximatley 350 fs, and an additional time constant of tau3 approximately 1 ps. The third time constant is only visible in the time-dependence of low kinetic energy electrons. Due to the dense manifold of excited states between 3.9 and 5 eV, known from ab initio calculations, the recorded time-resolved electron images show broad and unstructured bands. A clear population transfer between the states thus can not directly be observed. The fast deactivation process is linked to either a population transfer between the strongly coupled excited states between 3.9 and 5.0 eV or the movement of the produced wave packet out of the Franck-Condon region. Since the third long time constant is only visible for photoelectrons at low kinetic energy, evidence is given that this time constant corresponds to the lifetime of the lowest excited A 1A' state. The remaining time constant reflects a deactivation of the manifold of states in the range 3.9-5.0 eV down to the A 1A' state.     

Multiple Decay Mechanisms and 2D‐UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine‐Uracil Monophosphate

The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D‐UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine ¹L_a state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine ¹L_b and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter‐base hydrogen transfer and decay to the ground state through a conical intersection, or it can yield a long‐lived minimum stabilized by a hydrogen bond between the two ribose rings. This suggests that the ¹L_b, S(U) and CT states of the stacked conformer may all contribute to the experimental lifetimes of 18 and 240 ps. We have also simulated the time evolution of the 2D‐UV spectra and provide the specific fingerprint of each species in a recommended probe window between 25 000 and 38 000 cm^?1 in which decongested, clearly distinguishable spectra can be obtained. This is expected to allow the mechanistic scenarios to be discerned in the near future with the help of the corresponding experiments. Our results reveal the complexity of the photophysics of the relatively small ApU system, and the potential of 2D‐UV spectroscopy to disentangle the photophysics of multichromophoric systems.     

Inertial effects on the intramolecular vibrational energy redistribution and nonadiabatic photoisomerization of a 2,3-substituted 1,3-butadiene: a quasi-classical CASSCF dynamics study

Quasi-classical CASSCF trajectory calculations have been carried out on s-cis-1,3-butadiene and substituted 2,3-dideuterio-1,3-butadiene (DDB) to assess the inertial effect on the ultrafast nonadiabatic deactivation of their first singlet excited states. Calculations indicate that even this modest increase in the mass of the 2,3-substituents noticeably affects the photodynamics of cis --> trans isomerization, by reducing the efficiency of the vibrational energy leakage between the initial relaxation and subsequent nonadiabatic decay modes. In qualitative agreement with experimental findings on related 1,3-dienes, the slowing down of the intramolecular vibrational energy redistribution (IVR) upon substitution results in extended excited-state lifetimes and reorients the photoregioselectivity toward cis rotamers and cyclic products.     

外电场下氮化铝分子结构和光谱研究

以6-311＋G(2DF)为基函数, 采用密度泛函B3P86的方法研究了外电场作用下氮化铝(AlN)基态分子的几何结构、HOMO能级、LUMO能级、能隙及谐振频率. 结果表明, 外电场的大小和方向对AlN分子基态的这些性质有明显影响. 在所加的电场范围内, 随着外电场的增大分子键长减小, 谐振频率增大, 总能量升高, 在F＝0.02 a.u.时能量达到最大, 为－297.4217 a.u., 此后继续增大电场强度, 系统总能量则开始降低; EH 和EL 随着电场的增加均逐渐增大, 在 F＝0.01 a.u.时, EH 和EL均取得最大值, 分别为－0.2776和－0.0828 a.u., 随着电场的继续增大, 能级EH和EL均逐渐减小, 而能隙在外电场增大的过程中始终处于减小趋势.     

β‐to‐β 2,5‐Pyrrolylene‐Linked Cyclic Porphyrin Oligomers

β‐to‐β 2,5‐Pyrrolylene linked cyclic porphyrin oligomers have been synthesized by Suzuki–Miyaura coupling of 2,5‐diborylpyrrole and 3,7‐dibromoporphyrin. The cyclic porphyrin oligomers exhibit roughly coplanar structures, strong excitonic coupling, small electrochemical HOMO–LUMO gaps, and ultrafast excitation energy transfer between the neighboring porphyrins via the pyrrolylene bridge.     

Unprecedented π···π interaction between an aromatic ring and a pseudo-aromatic ring formed through intramolecular H-bonding in a bidentate Schiff base ligand: crystal structure and DFT calculations

A combination of a single crystal X-ray diffraction study and density functional theory calculations has been applied to a bidentate Schiff base compound to elucidate different cooperative non-covalent interactions involved in the stabilization of the keto form over the enol one in the solid state. The single crystal X-ray structure reveals a remarkable supramolecular assembly of the keto form through a cyclic hydrogen bonded dimeric motif. The most interesting feature in the supramolecular assembly is the formation of a 'dimer of dimer' motif by π···π, CH···π and N···O/O···O interactions in which the π···π interaction involving the aromatic phenyl ring and the intramolecularly hydrogen bonded pseudo-aromatic ring of the keto form lying just above or below the phenyl ring of the other dimer seems to be unprecedented. The optimized geometry of the hydrogen bonded dimeric motif of the keto form of the organic molecule has been obtained by DFT calculations and agrees very well with that found within the crystalline state. The X-ray crystallographic geometry of the 'dimer of dimer' has also been computed, which shows that in the HOMO, the π electrons are localized in the phenyl rings away from each other, while in the LUMO, there is a strong π-π interaction between the phenyl ring of one dimer with the pseudo-aromatic ring of another dimer with an energy estimated to be 7.95 kJ mol(-1). Therefore, on HOMO → LUMO excitation there is localization of π electrons in the central part of the complex moiety which plays a stabilizing role of the dimer of dimer motif in the solid state.     

Ultrafast energy delocalization and electron transfer dynamics in 2-aminopurine-containing trinucleotides

The fate of electronically excited states in DNA base stacks is of tremendous importance for subsequent photochemical damage reactions in the genome. In this study we present a femtosecond broadband pump-probe study on the adenine isomer 2-aminopurine (Ap) incorporated into trinucleotides. After selective excitation of Ap we can monitor energy delocalization between neighboring Ap moieties as well as excited state electron transfer, depending on the sequence of the trinucleotide. Our results establish the time scale for intrastand excimer formation and reveal the lifetime of the excimer state.     

Electron-phonon interactions in photoinduced excited electronic states in fluoroacenes

The electron-phonon coupling constants [l(B1u(HOMO-->LUMO))] in the photoinduced excited electronic states in fluoroacenes are estimated and compared with those in the monoanions (l(LUMO)) and cations (l(HOMO)). The l(B1u(HOMO-->LUMO)) values are much larger than the l(LUMO) and l(HOMO) values in fluoroacenes. Furthermore, the Coulomb pseudopotential mu* values for the excited electronic states are estimated to be smaller than those for the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) is the main reason why the electron-phonon coupling constants and the mu* values are larger and smaller, respectively, in the photoinduced excited electronic states than in the monoanions and cations. The possible electron pairing and Bose-Einstein condensation in the excited electronic states of fluoroacenes are discussed. Because of larger electron-phonon coupling constants and smaller mu* values in the excited electronic states than in the charged states, the conditions under which the electron-electron interactions become attractive can be more easily realized, in principle, in the excited electronic states than in the charged states in fluoroacenes. The l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution, even though the l(LUMO) and l(HOMO) values significantly increase by H-F substitution in acenes. Antibonding interactions between carbon and fluorine atoms in the HOMO and LUMO are the main reason why the l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution in acenes.     

Ultrafast nonradiative decay of electronically excited States of malachite green: ab initio calculations

We have investigated the nonradiative deactivation process of malachite green in the singlet excited states, S(1) and S(2), by high-level ab initio quantum chemical calculations using the CASPT2//CASCF approach. The deactivation pathways connecting the Franck-Condon region and conical intersection regions are identified. The initial population in the S(1) state is on a flat surface and the relaxation involves a rotation of phenyl rings, which leads the molecule to reach the conical intersection between the S(1) and S(0) states, where it efficiently decays back to the ground state. There exists a small barrier connecting the Franck-Condon and conical intersection regions on the S(1) potential energy surface. The decay mechanism from the S(2) state also involves the twisting motion of phenyl rings. In contrast to the excitation to the S(1) state, the initial population is on a downhill ramp potential and the barrierless relaxation through the rotation of substituted phenyl rings is expected. During the course of relaxation, the molecule switches to the S(1) state at the conical intersection between S(2) and S(1), and then it decays back to the ground state through the intersection between S(1) and S(0). In relaxation from both S(1) and S(2), large distortion of phenyl rings is required for the ultrafast nonradiative decay to the ground state.     

Trans-cis photoisomerization of azobenzene by n→π* excitation:A semiclassical dynamics study

A realistic dynamics simulation study is reported for the trans-cis photoisomerization of azobenzene triggered by the n→π*excitation and the results show that the formation of cis isomer follows the rotational motion around the N=N bond.The simulation find that the CNN bond angle bending vibrations also play a significant role in the vibronic coupling between the HOMO and LUMO,which essentially leads a nonadiabatic transition of the molecule to the electronic ground state.     

The electronic spectra of the sandwich stacked PFBT: a theoretical study

Stacked models that include 9,9'-bis(6'-N,N,N-trimethylammonium)hexyl]fluorene-co-alt-4,7-(2,1,3-benzothiadiazole)dibromide (F(BT)F) monomer sandwiched between two stacked 2,1,3-benzothiadiazole (BT) units were explored using theoretical approaches. Molecular structures and the optical characteristics of the investigated species were investigated at the M06-2X/6-311G(d,p)//TD-M06-2X/6-311G(d,p) level of theory. In all models, the electronic excitation to the lowest singlet ππ* excited state (S1(ππ*)) is governed by the highest occupied molecular orbital to lowest unoccupied molecular orbital (HOMO → LUMO) transitions. The obtained results suggest that stacking interaction might have only minor effects on the transition energy for both absorption and emission processes. Instead, the reduction in the excitation energy of the stacked complexes should be attributed to the dipole-dipole interaction. The larger the interaction energy of the stacked models, the bigger the observed differences between absorption-emission energies. The presence of the solvation medium with small dielectric constant may increase the absorption-emission energy differences. It is expected that the largest absorption-emission shift can be observed in the benzene solution.