*J Phys Chem A ; 125(40): 8912-8924, 2021 Oct 14.*

##### RESUMO

In this contribution we present a quantum dynamical study of the photoexcited hydrogen bonded base pair adenine-thymine (AT) in a Watson-Crick arrangement. To that end, we parametrize Linear Vibronic Coupling (LVC) models with Time-Dependent Density Functional Theory (TD-DFT) calculations, exploiting a fragment diabatization scheme (FrD) we have developed to define diabatic states on the basis of individual chromophores in a multichromophoric system. Wavepacket propagations were run with the multilayer extension of the Multiconfiguration Time-Dependent Hartree method. We considered excitations to the three lowest bright states, a ππ* state of thymine and two ππ* states (La and Lb) of adenine, and we found that on the 100 fs time scale the main decay pathways involve intramonomer population transfers toward nπ* states of the same nucleobase. In AT this transfer is less effective than in the isolated nucleobases, because hydrogen bonding destabilizes the nπ* states. The population transfer to the A â T charge transfer state is negligible, making the ultrafast (femtosecond) decay through the proton coupled electron transfer mechanism unlikely, in line with experimental results in apolar solvents. The excitation energy transfer is also very small. We carefully compare the predictions of LVC Hamiltonians obtained with different sets of diabatic states, defined so to match either local states of the two separated monomers or the base pair adiabatic states in the Franck-Condon region. To that end we also extend the flexibility of the FrD-LVC approach, introducing a new strategy to define fragments diabatic states that account for the effect of the rest of the multichromohoric system through a Molecular Mechanics potential.

*Phys Chem Chem Phys ; 23(31): 16551-16563, 2021 Aug 12.*

##### RESUMO

We report a computational study on vibronic effects in the spectroscopy, photoinduced processes and decay back to the ground state of aza[7]helicene, a helicene with an unusually high fluorescence quantum yield (QY = 0.39). In a first step, we compute and assign the absorption and electronic circular dichroism (ECD) spectra in its full frequency range from 2.7 to 5.0 eV, accounting for nonadiabatic effects. Then we compute the quantum dynamics of the cascade of ultrafast internal conversions of the highly-excited singlet states to the lowest-energy one S1. Finally we adopt Fermi golden rule rates to compute the QY of the dye, taking into account the competition between the radiative decay and the nonradiative decays to the ground state and to the energy-accessible triplet states. We use time-dependent density functional theory (TD-DFT), including solvent (dichloromethane) effects within the polarizable continuum model, to parameterize a linear vibronic coupling (LVC) model involving the first lowest 12 singlet states and all the normal coordinates. Nonadiabatic spectra and internal conversions dynamics are then computed through wavepacket propagations with the Multilayer (ML) extension of the Multiconfigurational Time Dependent Hartree method (ML-MCTDH). We highlight the molecular vibrations playing a major role in determining the shape of the spectra and analyse the effect of inter-state couplings. At the same time we report a breakdown of perturbative Herzberg-Teller approach. The computed QY is in perfect agreement with experiment and allows us to ascertain that intersystem crossings are the processes limiting the fluorescence from S1. They involve the three lowest triplet states and are made effective by spin-orbit coupling and vibronic effects.

*J Chem Theory Comput ; 17(8): 4660-4674, 2021 Aug 10.*

##### RESUMO

We introduce a method (FrD-LVC) based on a fragment diabatization (FrD) for the parametrization of a linear vibronic coupling (LVC) model suitable for studying the photophysics of multichromophore systems. In combination with effective quantum dynamics (QD) propagations with multilayer multiconfigurational time-dependent Hartree (ML-MCTDH), the FrD-LVC approach gives access to the study of the competition between intrachromophore decays, like those at conical intersections, and interchromophore processes, like exciton localization/delocalization and the involvement of charge-transfer (CT) states. We used FrD-LVC parametrized with time-dependent density functional theory (TD-DFT) calculations, adopting either CAM-B3LYP or ωB97X-D functionals, to study the ultrafast photoexcited QD of a guanine-cytosine (GC) hydrogen-bonded pair, within a Watson-Crick arrangement, considering up to 12 coupled diabatic electronic states and the effect of all of the 99 vibrational coordinates. The bright excited states localized on C and, especially, on G are predicted to be strongly coupled to the G â C CT state, which is efficiently and quickly populated after an excitation to any of the four lowest energy bright local excited states. Our QD simulations show that more than 80% of the excited population on G and â¼50% of that on C decay to this CT state in less than 50 fs. We investigate the role of vibronic effects in the population of the CT state and show that it depends mainly on its large reorganization energy so that it can occur even when it is significantly less stable than the bright states in the Franck-Condon region. At the same time, we document that the formation of the GC pair almost suppresses the involvement of dark nπ* excited states in the photoactivated dynamics.

##### Assuntos

Citosina/química , Guanina/química , Pareamento de Bases , Citosina/metabolismo , Teoria da Densidade Funcional , Guanina/metabolismo , Ligação de Hidrogênio*Phys Chem Chem Phys ; 23(14): 8181-8199, 2021 Apr 14.*

##### RESUMO

We concisely review the main methodological approaches to model nonadiabatic dynamics in isotropic solutions and their applications. Three general classes of models are identified as the most used to include solvent effects in the simulations. The first model describes the solvent as a set of harmonic collective modes coupled to the solute degrees of freedom, and the second as a continuum, while the third explicitly includes solvent molecules in the calculations. The issues related to the use of these models in semiclassical and quantum dynamical simulations are discussed, as well as the main limitations and perspectives of each approach.

*Molecules ; 26(6)2021 Mar 20.*

##### RESUMO

We have recently proposed a protocol for Quantum Dynamics (QD) calculations, which is based on a parameterisation of Linear Vibronic Coupling (LVC) Hamiltonians with Time Dependent (TD) Density Functional Theory (TD-DFT), and exploits the latest developments in multiconfigurational TD-Hartree methods for an effective wave packet propagation. In this contribution we explore the potentialities of this approach to compute nonadiabatic vibronic spectra and ultrafast dynamics, by applying it to the five nucleobases present in DNA and RNA. For all of them we computed the absorption spectra and the dynamics of ultrafast internal conversion (100 fs timescale), fully coupling the first 2-3 bright states and all the close by dark states, for a total of 6-9 states, and including all the normal coordinates. We adopted two different functionals, CAM-B3LYP and PBE0, and tested the effect of the basis set. Computed spectra are in good agreement with the available experimental data, remarkably improving over pure electronic computations, but also with respect to vibronic spectra obtained neglecting inter-state couplings. Our QD simulations indicate an effective population transfer from the lowest energy bright excited states to the close-lying dark excited states for uracil, thymine and adenine. Dynamics from higher-energy states show an ultrafast depopulation toward the more stable ones. The proposed protocol is sufficiently general and automatic to promise to become useful for widespread applications.

##### Assuntos

DNA/química , Modelos Químicos , RNA/química , Adenina/química , Citosina/química , Timina/química , Uracila/química*J Chem Phys ; 154(10): 104106, 2021 Mar 14.*

##### RESUMO

With this work, we present a protocol for the parameterization of a Linear Vibronic Coupling (LVC) Hamiltonian for quantum dynamics using highly accurate multiconfigurational electronic structure methods such as RASPT2/RASSCF, combined with a maximum-overlap diabatization technique. Our approach is fully portable and can be applied to many medium-size rigid molecules whose excited state dynamics requires a quantum description. We present our model and discuss the details of the electronic structure calculations needed for the parameterization, analyzing critical situations that could arise in the case of strongly interacting excited states. The protocol was applied to the simulation of the excited state dynamics of the pyrene molecule, starting from either the first or the second bright state (S2 or S5). The LVC model was benchmarked against state-of-the-art quantum mechanical calculations with optimizations and energy scans and turned out to be very accurate. The dynamics simulations, performed including all active normal coordinates with the multilayer multiconfigurational time-dependent Hartree method, show good agreement with the available experimental data, endorsing prediction of the excited state mechanism, especially for S5, whose ultrafast deactivation mechanism was not yet clearly understood.

*J Chem Theory Comput ; 17(3): 1638-1652, 2021 Mar 09.*

##### RESUMO

We present a computational study of the one-photon and excited-state absorption (ESA) from the two lowest energy excited states of uracil in the gas phase: an nπ* dark state (1n) and the lowest energy bright ππ* state (1π). The predictions of six different linear response electronic structure methods, namely, TD-CAM-B3LYP, EOM-CCSD, EOM-CC3, ADC(2), ADC(2)-x, and ADC(3) are critically compared. In general, the spectral shapes predicted by TD-CAM-B3LYP, EOM-CCSD, EOM-CC3, and ADC(3) are fairly similar, though the quality of TD-CAM-B3LYP slightly deteriorates in the high-energy region. By computing the spectra at some key structures on different potential energy surfaces (PES), that is, the Franck-Condon point, the 1n minimum, and structures representative of different regions of the 1π PES, we obtain important insights into the shift of the ESA spectra, following the motion of the wavepacket on the excited-state PES. Though 1π has larger ESA than 1n, some spectral regions are dominated by these latter signals. Aside from its methodological interest, we thus obtain interesting indications to interpret transient absorption spectra to disentangle the photoactivated dynamics of nucleobases.

##### Assuntos

Teoria da Densidade Funcional , Uracila/química , Elétrons , Gases/química*J Chem Theory Comput ; 17(3): 1691-1700, 2021 Mar 09.*

##### RESUMO

Hexahelicene is a prototype of an extended π-conjugated system with axial chirality. Its absorption (ABS) and electronic circular dichroism (ECD) spectra show vibronic features and strong nonadiabatic effects, challenging currently available computational methods. Here, we compute the nonadiabatic ABS and ECD vibronic spectra of hexahelicene in the full energy range, covering â¼2 eV and 14-18 coupled electronic states, including all of the relevant nuclear coordinates. To this end, we exploit a recently proposed protocol that uses time-dependent density functional theory to parameterize linear vibronic coupling models comprising several electronic states. Spectra are computed through quantum dynamical propagations with multiconfigurational time-dependent Hartree methods. Our results nicely reproduce the experimental spectra providing an assignment of the main observed bands. On the contrary, we document that the application of the Herzberg-Teller intensity-borrowing theory leads to large artifacts. The proposed approach is of general applicability for rigid systems and represents a viable tool for studying the photophysical properties of π-conjugated systems characterized by a dense manifold of interacting electronic states.

*J Am Chem Soc ; 143(2): 983-991, 2021 01 20.*

##### RESUMO

Here we report the synthesis of two polyhelicene frameworks consisting, from end-to-end, of 18 and 24 fused benzene rings. The latter exhibits the largest electronic circular dichroism in the visible spectrum of any molecule. These shape-persistent helical nanoribbons incorporate multiple helicenes, a class of contorted polycyclic aromatic molecules consisting of ortho-annulated rings. These conjugated, chiral molecules have interesting chemical, biological, and chiroptical properties; however, there are very few helicenes with extraordinary chiroptical response over a broad range of the visible spectrum-a key criterion for applications such as chiral optoelectronics. In this report, we show that coupling the polyhelicene framework with multiple perylene-diimide subunits elicits a significant chiroptic response. Notably, the molar circular dichroism increases faster than the absorptivity of these molecules as their helical axis lengthens. Computational analysis reveals that the greatly amplified circular dichroism arises from exciton-like interactions between the perylene-diimide and the helicene moieties. We predict that even greater chiroptic enhancement will result from further axial elongation of these nanoribbons, which can be readily enabled via the iterative synthetic method presented herein.

##### Assuntos

Nanoestruturas/química , Compostos Policíclicos/química , Teoria da Densidade Funcional , Estrutura Molecular , Compostos Policíclicos/síntese química , Estereoisomerismo*J Chem Theory Comput ; 17(1): 405-415, 2021 Jan 12.*

##### RESUMO

We here propose a general and flexible approach, based on fragment diabatization, which incorporates charge transfer states and significantly increases the reliability of excitonic Hamiltonians for systems where the chromophores are very close. This model (FrDEx) is used to compute the electronic circular dichroism and absorption spectra of two prototype guanine-rich DNA sequences folded in quadruple helices (GQs), i.e., a fragment of the human telomeric sequence (Tel21, antiparallel), and (TGGGGT)4 (TG4T, parallel). Calculations on different subsets of Tel21 and TG4T, from dimers to tetramers, show that FrDEx provides spectra close to the reference full quantum mechanical (QM) ones (obtained with time-dependent density functional theory), with significant improvements with respect to "standard" excitonic Hamiltonians. Furthermore, these tests enable the most cost-effective procedure for the whole GQ to be determined. FrDEx spectra of Tel21 and TG4T are also in good agreement with the QM and experimental ones and give access to interesting insights into the chemical-physical effects modulating the spectral signals. FrDEx could be profitably used to investigate many other biological and nanotechnological materials, from DNA to (opto)electronic polymers.

##### Assuntos

Quadruplex G , Guanina/química , DNA/química , Dimerização , Elétrons , Modelos Moleculares , Teoria Quântica*Phys Chem Chem Phys ; 22(45): 26525-26535, 2020 Nov 25.*

##### RESUMO

We study the ultrafast dynamics of 1,5-dimethyl-cytosine, a model for 5-methyl-cytidine, after photoexcitation to the first two bright ππ* states, focusing on the possible population transfer to dark nπ* states. To that end we propagate the initial wave packets on the coupled potential energy surfaces of the seven lowest energy excited states modelled with a diabatic linear vibronic coupling (LVC) model, considering all the vibrational coordinates. Time-evolution is computed by the multilayer version of the multiconfigurational time dependent Hartree (ML-MCTDH) method. The LVC Hamiltonian is parametrized with time-dependent density functional theory (TD-DFT) calculations adopting PBE0 and CAM-B3LYP functionals, which provide a different energy gap between the lowest energy nπ* states and the spectroscopic ππ* state. Population of the lowest ππ* flows to a dark nπ* state which involves a lone pair (LP) of the carbonyl oxygen (nOπ*), but the extent of such transfer is much larger according to PBE0 than to CAM-B3LYP. Photoexcitation to the second bright state gives rise to much richer dynamics with an ultrafast (50 fs) complete decay to the lowest ππ*, to nOπ* and to another nπ* in which the excited electron comes from the LP of the ring nitrogen. We perform a detailed analysis of the vibronic dynamics both in terms of normal modes and valence coordinates (bond lengths and angles). The comparison with the analogous dynamics in 1-methyl-cytosine, a model for cytidine, provides insights into the effect of methylation at carbon 5 on the electronic and nuclear dynamics.

##### Assuntos

Citosina/química , Gases/química , Modelos Químicos , Citidina/análogos & derivados , Citidina/química , Elétrons , Epigênese Genética , Luz , Análise Espectral , Vibração*J Chem Theory Comput ; 16(11): 7061-7077, 2020 Nov 10.*

##### RESUMO

The optical absorption spectrum of a perylene diimide (PDI) dye in acetonitrile solution is simulated using the recently developed (J. Chem. Theory Comput. 2020, 16, 1215-1231) Ad-MD|gVH method. This mixed quantum-classical (MQC) approach is based on an adiabatic (Ad) separation of soft(classical)/stiff(quantum) nuclear degrees of freedom and expresses the spectrum as a conformational average (over the soft coordinates) of vibronic spectra (for the stiff coordinates) obtained through the generalized vertical Hessian (gVH) vibronic approach. The average is performed over snapshots extracted from classical molecular dynamics (MD) runs, performed with a specifically parameterized quantum-mechanically derived force field (QMD-FF). A comprehensive assessment of the reliability of different approaches, designed to reproduce spectral shapes of flexible molecules, is here presented. First, the differences in the sampled configurational space and their consequences on the prediction of the absorption spectra are evaluated by comparing the results obtained by means of the specific QMD-FF and of a general-purpose transferable FF with those of a reference ab initio MD (AIMD) in the gas phase, in both a purely classical scheme (ensemble average) and in the Ad-MD|gVH framework. Next, classical ensemble average and MQC predictions are also obtained for the PDI dynamics in solution and compared with the results of a â³staticâ³ approach, based on vibronic calculations carried out on a single optimized perylene diimide structure. In the classical ensemble average approach, the remarkably different samplings obtained with the two FFs lead to sizeable changes in both position and intensity of the predicted spectra, with the one computed along the QMD-FF trajectory closely matching its AIMD counterpart. Conversely, at the Ad-MD|gVH level of theory, the different samplings deliver very similar vibronic spectra, indicating that the error found in the absorption spectra obtained with the general-purpose FF mainly concerns the stiff modes. In fact, it can be effectively corrected by the quadratic extrapolation performed by gVH to locate the minima of the ground- and excited-state potential energy surfaces along such coordinates. Furthermore, in the perspective of studying the self-assembling process of PDI dyes and the vibronic spectra of large-size aggregates, the use of a molecule-specific QMD-FF also appears mandatory, considering the significant errors found in the GAFF trajectory in the flexible lateral chain populations, which dictate the supramolecular aggregation properties.

*Chemistry ; 26(72): 17342-17349, 2020 Dec 23.*

##### RESUMO

Several theoretical studies have proposed strategies to generate helical molecular orbitals (Hel-MOs) in [n]cumulenes and oligoynes. While chiral even-[n] cumulenes feature Hel-MOs, odd-[n] cumulenes may also present them if the terminal groups lie in different planes. However, the proposed systems have been either experimentally unfeasible or resulted in opposite pseudo-degenerated Hel-MOs. We hereby demonstrate the introduction of a remarkable energy difference between helical orbitals of opposite twist by fixing the torsion angle between the terminal groups in butadiyne fragments. To experimentally lock the conformation of the terminal groups, we designed and synthesized cyclic architectures by combining acetylenes with chiral spirobifluorenes. The high stability of these systems with distinct helical orbitals allowed their isolation and full characterization. In our view, these results constitute a step further in the development of real systems presenting helical molecular orbitals.

##### Assuntos

Alcinos , Polienos , Alcinos/química , Modelos Moleculares , Conformação Molecular , Polienos/química*J Chem Theory Comput ; 16(9): 5792-5808, 2020 Sep 08.*

##### RESUMO

The nonadiabatic quantum dynamics (QD) of cytosine and 1-methylcytosine in the gas phase is simulated for 250 fs after a photoexcitation to one of the first two bright states. The nuclear wavepacket is propagated on the coupled diabatic potential energy surfaces of the lowest seven excited states, including ππ*, nπ*, and Rydberg states along all the vibrational degrees of freedom. We focus in particular on the interplay between the bright and the dark nπ* states, not considering the decay to the ground electronic state. To run these simulations, we implemented an automatic general procedure to parametrize linear vibronic coupling (LVC) models with time-dependent density functional theory (DFT) computations and interfaced it with Gaussian package. The wavepacket was propagated with the multilayer version of the multiconfigurational time dependent Hartree method. Two different density functionals, PBE0 and CAM-B3LYP, which provide a different description of the relative stability of the lowest energy dark states, were used to parametrize the LVC Hamiltonian. Part of the photoexcited population on lowest HOMO-LUMO transition (πHπL*) decays within less than 100 fs to a nπ* state which mainly involves a promotion of an electron from the oxygen lone pair to the LUMO (nOπL*). The population of the second ππ* state decays almost completely, in <100 fs, not only to πHπL* and to nOπL* states but also to another nπL* state involving the nitrogen lone pair. The efficiency of the adopted protocol allowed us to check the accuracy of the predictions by repeating the QD simulations with different LVC Hamiltonians parametrized either at the ground-state minimum or at stationary structures of different relevant excited states.

*Chirality ; 32(7): 932-948, 2020 07.*

##### RESUMO

(R)-1-phenyl-ethanol (PhEtOH) and the different isomers of (R)-1-(chlorophenyl)ethanol (ClPhEtOH) exhibit very interesting electronic circular dichroism (ECD) in methanol. In all cases, the spectrum shows clear vibronic features, but it is monosignated and negative for PhEtOH and meta-ClPhEtOH, positive for the ortho isomer and bisignated for the para isomer. We used computational chemistry to rationalise this behaviour adopting CAM-B3LYP/def2-TZVP, describing the bulk solvent effects with polarizable continuum models and solute-solvent specific interactions with clusters comprising the solute and two solvent molecules. We adopted harmonic vibronic models to compute the ECD spectral shapes of all stable conformers, and we obtained the room-temperature spectra by Boltzmann average. Simulated spectra are in very good agreement with experiment and allow us to rationalise their difference in terms of the relevance of Franck-Condon (FC) and Herzberg-Teller (HT) intensity-borrowing contributions, modulated by the substituent effect. The bisignated shape of the spectrum of para-ClPhEtOH arises from the competition of opposite-sign FC and HT bands, promoted by different vibrational modes. Due to the challenges we document in computing its ECD spectrum, para-ClPhEtOH represents a good test case to help the development of novel methodologies for an improved description of weak vibronic ECD spectra of flexible systems in explicit solvents.

*J Chem Phys ; 152(5): 054107, 2020 Feb 07.*

##### RESUMO

For the rational design of new fluorophores, reliable predictions of fluorescence quantum yields from first principles would be of great help. However, efficient computational approaches for predicting transition rates usually assume that the vibrational structure is harmonic. While the harmonic approximation has been used successfully to predict vibrationally resolved spectra and radiative rates, its reliability for non-radiative rates is much more questionable. Since non-adiabatic transitions convert large amounts of electronic energy into vibrational energy, the highly excited final vibrational states deviate greatly from harmonic oscillator eigenfunctions. We employ a time-dependent formalism to compute radiative and non-radiative rates for transitions and study the dependence on model parameters. For several coumarin dyes, we compare different adiabatic and vertical harmonic models (AS, ASF, AH, VG, VGF, and VH), in order to dissect the importance of displacements, frequency changes, and Duschinsky rotations. In addition, we analyze the effect of different broadening functions (Gaussian, Lorentzian, or Voigt). Moreover, to assess the qualitative influence of anharmonicity on the internal conversion rate, we develop a simplified anharmonic model. We address the reliability of these models considering the potential errors introduced by the harmonic approximation and the phenomenological width of the broadening function.

*J Chem Theory Comput ; 16(2): 1215-1231, 2020 Feb 11.*

##### RESUMO

We present a general mixed quantum classical method that couples classical molecular dynamics (MD) and vibronic models to compute the shape of electronic spectra of flexible molecules in the condensed phase without, in principle, any phenomenological broadening. It is based on a partition of the nuclear motions of the solute + solvent system in "soft" and "stiff" vibrational modes and an adiabatic hypothesis that assumes that stiff modes are much faster than soft ones. In this framework, the spectrum is rigorously expressed as a conformational integral of quantum vibronic spectra along the stiff coordinates only. Soft modes enter at the classical level through the conformational distribution that is sampled with classical MD runs. In each configuration, reduced-dimensionality quadratic Hamiltonians are built in the space of the stiff coordinates only, thanks to a generalization of the Vertical Hessian harmonic model and an iterative application of projectors in internal coordinates to remove soft modes. Quantum vibronic spectra, specific for each sampled configuration of the soft coordinates, are then computed at the desired temperature with efficient time-dependent techniques, and the global spectrum simply arises from their average. For consistency of the whole procedure, classical MD runs are performed with quantum-mechanically derived force fields, parameterized at the same level of theory selected for generating the quadratic Hamiltonians along the stiff coordinates. Application to N-methyl-6-oxyquinolinium betaine in water, dithiophene in ethanol, and cyanidine in water is presented to show the performance of the method.

*J Phys Chem Lett ; 10(14): 4089-4094, 2019 Jul 18.*

##### RESUMO

Time-resolved circular dichroism (TR-CD) is a powerful tool for probing conformational dynamics of biomolecules over large time scales that are crucial for establishing their structure-function relationship. However, such experiments, notably in the femtosecond regime, remain challenging due to their extremely weak signals, prone to polarization artifacts. By using binol and two bridged derivatives (PL1 and PL2) as chiral prototypes, we present here the first comprehensive study of this type in the middle UV, combining femtosecond TR-CD and quantum mechanical calculations (TD-DFT). We show that excitation of the three compounds induces large variations of their transient CD signals, in sharp contrast to those of their achiral transient absorption. We demonstrate that these variations arise from both the alteration of the electronic distribution and the dihedral angle in the excited state. These results highlight the great sensitivity of TR-CD detection to signals hardly accessible to achiral transient absorption.

*J Chem Theory Comput ; 15(2): 1242-1254, 2019 Feb 12.*

##### RESUMO

The absorption and magnetic circular dichroism (MCD) spectra of purine and of the purine nucleobases adenine and guanine have been calculated in gas phase at the Coupled Cluster Singles and Doubles (CCSD) and Resolution-of-Identity Singles and Approximate Doubles (RI-CC2) levels of theory. Exploiting a new development in the TURBOMOLE program package for computing vertical excitation energies and Faraday [Formula: see text] terms in an implicit solvent approximated by the conductor-like screening model (COSMO) at the CC2 level, we have investigated the solvent effects on the relative positions of the ππ* and nπ* electronic transitions in these three molecules and compared them to the corresponding vacuum results. In the case of adenine, we also included specific solvent effects with a small water cluster. The spectra obtained with the implicit model COSMO are in qualitative agreement with those obtained with explicit water molecules both with and without the inclusion of the bulk solvent effects via the continuum solvent model. This suggests that the inclusion of the electrostatic contributions of the solvent can provide a sufficiently accurate description of the absorption spectra for adenine. The results for purine, adenine, and guanine show that, after the inclusion of bulk solvation, the ππ* states shift to lower energies while at the same time nπ* states show a reversed behavior. The computed MCD spectra show the characteristic bisignate profile found experimentally in all cases, despite, for adenine, remarkable differences in the origin of the individual peaks for different computational methods. Therefore, the ability (or inability) of MCD to determine the relative stability of the La and Lb states is critically reassessed. According to our best estimate for adenine in aqueous solution, the La state is more stable than Lb.

##### Assuntos

Adenina/química , Guanina/química , Purinas/química , Dicroísmo Circular , Modelos Químicos , Modelos Moleculares , Teoria Quântica , Espectrofotometria Ultravioleta , Termodinâmica , Água/química*Phys Chem Chem Phys ; 20(34): 22260-22271, 2018 Aug 29.*

##### RESUMO

A three-step synthetic route to a structurally unique π-expanded pyrrolo[3,2-b]pyrrole derived bis-ketone has been developed. In contrast to all previous ladder-type pyrrolopyrroles, the new dye exhibits a low-energy absorption band in the visible region which is responsible for its red-purple color. Interestingly, even though the compound is centrosymmetric, this band coincides with the lowest energy two-photon absorption (TPA) transition. This non-typical behaviour has been computationally rationalized by finding two close lying excited states, one of which (S1) is active for OPA and the other (S2) for TPA processes, which arise from the mixing of two symmetric partial charge-transfer states. The ultrafast excited-state dynamics was characterized by means of transient absorption analysis. A relaxation process involving S1 symmetry breaking occurs in a few ps, leading to the formation of the lowest energy charge-transfer state. This is weakly emitting, with a measured lifetime in the order of tens of picoseconds. Interestingly, two-photon polymerization has been achieved using this new ketone. The high yield of radical photo-initiation upon two-photon excitation was demonstrated by the fabrication of woodpile photonic crystal templates by direct laser writing using a zirconium-silicon hybrid composite.