19 research outputs found
Multireference approaches for excited states of molecules
Understanding the properties of electronically excited states is a challenging task that becomes increasingly important for numerous applications in chemistry, molecular physics, molecular biology, and materials science. A substantial impact is exerted by the fascinating progress in time-resolved spectroscopy, which leads to a strongly growing demand for theoretical methods to describe the characteristic features of excited states accurately. Whereas for electronic ground state problems of stable molecules the quantum chemical methodology is now so well developed that informed nonexperts can use it efficiently, the situation is entirely different concerning the investigation of excited states. This review is devoted to a specific class of approaches, usually denoted as multireference (MR) methods, the generality of which is needed for solving many spectroscopic or photodynamical problems. However, the understanding and proper application of these MR methods is often found to be difficult due to their complexity and their computational cost. The purpose of this review is to provide an overview of the most important facts about the different theoretical approaches available and to present by means of a collection of characteristic examples useful information, which can guide the reader in performing their own applications
Photorelaxation Induced by Water–Chromophore Electron Transfer
Relaxation of photoexcited chromophores
is a key factor determining
diverse molecular properties, from luminescence to photostability.
Radiationless relaxation usually occurs through state intersections
caused by distortions in the nuclear geometry of the chromophore.
Using excited-state nonadiabatic dynamics simulations based on algebraic
diagrammatic construction, it is shown that this is the case of 9H-adenine
in water cluster, but not of 7H-adenine in water cluster. 7H-adenine
in water cluster relaxes via a state intersection induced by electron
transfer from water to the chromophore. This result reveals an unknown
reaction pathway, with implications for the assignment of relaxation
mechanisms of exciton relaxation in organic electronics. The observation
of photorelaxation of 7H-adenine induced by water–chromophore
electron transfer is a proof of principle calling for further computational
and experimental investigations to determine how common this effect
is
Spatial Factors for Triplet Fusion Reaction of Singlet Oxygen Photosensitization
First-principles
quantum-chemical description of photosensitized
singlet oxygen generation kinetics is challenging because of the intrinsic
complexity of the underlying triplet fusion process in a floppy molecular
complex with open-shell character. With a quantum-chemical kinetic
model specifically tailored to deal with this problem, the reaction
rates are investigated as a function of intermolecular incidence direction,
orientation, and distance between O<sub>2</sub> and the photosensitizer.
The adopted photosensitizer, 6-azo-2-thiothymine, combines practical
interest and prototypical variability. The study quantitatively determined
maximum singlet oxygen generation rates for 15 incidence/orientation
directions, showing that they span 5 orders of magnitude between the
largest and the smallest rate. Such information may provide a hands-on
guideline for the experimental molecular design of new photosensitizers
as well as further higher-level theoretical research
Divide-to-Conquer: A Kinetic Model for Singlet Oxygen Photosensitization
Photosensitized singlet oxygen generation
occurring in a PS–O<sub>2</sub> complex, where PS is a photosensitizer
chromophore, is a
weakly coupled intermolecular energy-transfer process, a still challenging
problem for theoretical chemistry. To investigate the reaction rate
directly from quantum-chemical calculations, we built a semiclassical
kinetic model that minimizes the computational effort for the calculation
of diabatic couplings, activation energies, and reorganization energies,
which are the components of the rate. The model splits the system
into sets of orthogonal coordinates, which are then explored to compute
the reaction rate. This model offers an effective way to evaluate
the reaction probability of singlet oxygen generation along different
directions and intramolecular distances of the PS–O<sub>2</sub> complex. The model can also be applied to other similar intermolecular
energy-transfer problems, to connect the reaction kinetics and quantum-chemical
calculations
Hot and Cold Charge-Transfer Mechanisms in Organic Photovoltaics: Insights into the Excited States of Donor/Acceptor Interfaces
The evolution of
the excited-state manifold in organic D/A aggregates
(e.g., the prototypical P3HT/PCBM) is investigated through a bottom-up
approach via first-principles calculations. We show how the excited-state
energies, the charge transfer (CT) states, and the electron–hole
density distributions are strongly influenced by the size, the orientation,
and the position (i.e., on-top versus on-edge phases) of P3HT/PCBM
domains. We discuss how the structural order influences the excited-state
electronic structure, providing an atomistic interpretation of the
photophysics of organic blends. We show how the simultaneous presence
of on-top and on-edge phases does not alter the optical absorption
spectrum of the blend but does affect the photophysics. Photovoltaic
processes such as (i) the simultaneous charge generation obtained
from hot and cold excitations, (ii) the instantaneous and delayed
charge separation, and (iii) the pump–push–probe charge
generation can be interpreted based on our study
Unveiling the Role of <i>Hot</i> Charge-Transfer States in Molecular Aggregates via Nonadiabatic Dynamics
Exciton dynamics governs energy transfer
and charge generation
in organic functional materials. We investigate high-energy nonadiabatic
excited-state dynamics for a bithiophene dimer to describe time-dependent
excitonic effects in molecular aggregates. We show that the lowest
excited states are populated on the subpicosecond time scale. These
states are localized and unproductive in terms of charge separation.
Productive high-energy charge-transfer (CT) states are populated within
50 fs during exciton deactivation, but they are short-lived (∼100
fs) and quickly transfer their population to lower states. Our simulations
offer molecular-level insights into ultrafast photoinduced charge
separation potentially triggered by <i>hot</i> CT states
in solid-state organic materials. Design rules are suggested to increase <i>hot</i> exciton lifetimes, favoring the population of CT states
as gateways for direct charge generation. These rules may boost the
CT quantum yield by depleting unproductive recombination channels
Theoretical Characterization of Absorption and Emission Spectra of an Asymmetric Porphycene
The electronic ground and excited states of an asymmetric porphycene,
9-amino-2,7,12,17-tetraphenylporphycene (9-ATPPo), are investigated
by electronic structure calculations. Different tautomers are considered
to address their contributions to the photophysics of 9-ATPPo. Tautomerization
pathways on the ground and excited states are constructed between
different isomers. It is found that two trans tautomers are mainly
responsible for the absorption and emission spectra of 9-ATPPo. These
calculations provide a molecular mechanism to explain recent experimental
observations, which show a highly complex Q-band structure in the
absorption spectrum and pronounced dual fluorescence in the emission
spectrum. Furthermore, the current work shows that tautomerization
takes place under the assistance of cavity deformations and that a
nonradiative process occurs through weak interstate nonadiabatic couplings
near the S<sub>1</sub> minimum rather than strong ones near conical
intersections
Nonadiabatic Photodynamics of a Retinal Model in Polar and Nonpolar Environment
The nonadiabatic photodynamics of
the <i>all-trans</i>-2,4-pentadiene-iminium cation (protonated
Schiff base 3, PSB3) and
the <i>all-trans</i>-3-methyl-2,4-pentadiene-iminium cation
(MePSB3) were investigated in the gas phase and in polar (aqueous)
and nonpolar (<i>n</i>-hexane) solutions by means of surface
hopping using a multireference configuration-interaction (MRCI) quantum
mechanical/molecular mechanics (QM/MM) level. Spectra, lifetimes for
radiationless deactivation to the ground state, and structural and
electronic parameters are compared. A strong influence of the polar
solvent on the location of the crossing seam, in particular in the
bond length alternation (BLA) coordinate, is found. Additionally,
inclusion of the polar solvent changes the orientation of the intersection
cone from sloped in the gas phase to peaked, thus enhancing considerably
its efficiency for deactivation of the molecular system to the ground
state. These factors cause, especially for MePSB3, a substantial decrease
in the lifetime of the excited state despite the steric inhibition
by the solvent
Classification of doubly excited molecular electronic states
Electronic states with partial or complete doubly excited character play a crucial role in many areas, such as singlet fission and non-linear optical spectroscopy. Although doubly excited states have been studied in polyenes and related systems for many years, the assignment as singly vs. doubly excited, even in the simplest case of butadiene, has sparked controversies. So far, no well-defined framework for classifying doubly excited states has been developed, and even more, there is not even a well-accepted definition of doubly excited character as such. Here, we present a solution: a physically motivated definition of doubly excited character based on operator expectation values and density matrices, which works independently of the underlying orbital representation, avoiding ambiguities that have plagued earlier studies. Furthermore, we propose a classification scheme to differentiate three cases: (i) two single excitations occurring within two independent pairs of orbitals leaving four open shells (DOS), (ii) the promotion of both electrons to the same orbital, producing a closed-shell determinant (DCS), and (iii) a mixture of singly and doubly excited configurations not aligning with either one of the previous cases (Dmix). We highlight their differences in underlying energy terms and explain their signatures in practical computations. The three cases are illustrated through various high-level computational methods using dimers for DOS, polyenes for Dmix, and cyclobutane and tetrazine for DCS. The conversion between DOS and DCS is investigated using a well-known photochemical reaction, the photodimerization of ethylene. This work provides a deeper understanding of doubly excited states and may guide more rigorous discussions toward improving their computational description while also giving insight into their fundamental photophysics. </p
Photochemical Deactivation Process of HCFC-133a (C<sub>2</sub>H<sub>2</sub>F<sub>3</sub>Cl): A Nonadiabatic Dynamics Study
The
photochemical deactivation process of HCFC-133a (C<sub>2</sub>H<sub>2</sub>F<sub>3</sub>Cl) was investigated by computing excited-state
properties with a number of single-reference methods, including coupled
cluster to approximated second order (CC2), algebraic diagrammatic
construction to second order (ADC(2)), and time-dependent density
functional theory (TDDFT). Excited states calculated with these methods,
especially TDDFT, show good agreement with our previous multireference
configuration interaction (MR-CISD) results. All tested methods were
able to correctly predict the properties of the main series of excited
states, the n-σ*, n-4p, and n-4s. Nonadiabatic dynamics in the
gas phase considering 14 electronic states was simulated with TDDFT
starting at the 10 ± 0.25 eV spectral window, to be compared
to experimental data measured after 123.6 nm excitation. The excited-state
lifetime is 137 fs. Internal conversion to the ground state occurred
through several different reaction pathways with different products,
including atomic elimination (Cl, F, or H), multifragmentation mechanisms
(Cl+F, Cl+H, or F+H), and CC bond-fission mechanisms (alone or with
Cl or H elimination). The main photochemical channels observed were
Cl, Cl+H, and Cl+F eliminations, representing 54% of all processes