Basile F. E. Curchod

Basile F. E. Curchod
University of Bristol | UB · School of Chemistry

PhD in Chemistry

About

109
Publications
18,128
Reads
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6,831
Citations
Additional affiliations
March 2022 - present
University of Bristol
Position
  • Professor (Associate)
August 2021 - February 2022
Durham University
Position
  • Professor (Associate)
November 2017 - August 2021
Durham University
Position
  • Professor (Assistant)
Education
May 2009 - September 2013
École Polytechnique Fédérale de Lausanne
Field of study
  • Theoretical Chemistry
September 2007 - March 2009
October 2004 - July 2007

Publications

Publications (109)
Article
Full multiple spawning is a formally exact method to describe the excited-statedynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generaliz...
Article
Conical intersections represent critical topological features of potential energy surfaces and open ultrafast nonradiative deactivation channels for photoexcited molecules. In the following, we investigate how this funneling picture is transposed in the eyes of the exact factorization formalism for a two-dimensional model system. The exact factoriz...
Article
Full-text available
In this work, we present a complete derivation of the NonAdiabatic Bohmian DYnamics (NABDY) equations of motion. This approach naturally emerges from a transformation of the molecular time-dependent Schrödinger equation in the adiabatic representation of the electronic states. The numerical implementation of the method is discussed while simple non...
Article
Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of the exact factorization of the molecular wavefunction. In particular, we focus our attention on the shape of t...
Article
Full-text available
Dye-sensitized solar cells have gained widespread attention in recent years because of their low production costs, ease of fabrication and tunable optical properties, such as colour and transparency. Here, we report a molecularly engineered porphyrin dye, coded SM315, which features the prototypical structure of a donor-π-bridge-acceptor and both m...
Article
Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-20 -yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and...
Article
Herein, we expose how the antagonistic relationship between solid‐state luminescence and photocyclization of oligoaryl alkenes chromophores is modulated by the conjugation length of their alkenyl backbones. Heptaaryl cycloheptatriene molecular rotors exhibit aggregation‐induced emission characteristics. We show that their emission is turned off upo...
Article
Herein, we expose how the antagonistic relationship between solid‐state luminescence and photocyclization of oligoaryl alkenes chromophores is modulated by the conjugation length of their alkenyl backbones. Heptaaryl cycloheptatriene molecular rotors exhibit aggregation‐induced emission characteristics. We show that their emission is turned off upo...
Article
Full-text available
The photochemistry of pyruvic acid has attracted much scientific interest because it is believed to play critical roles in atmospheric chemistry. However, under most atmospherically relevant conditions, pyruvic acid deprotonates to form its conjugate base, the photochemistry of which is essentially unknown. Here, we present a detailed study of the...
Article
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The Born-Oppenheimer picture has forged our representation and interpretation of photochemical processes, from photoexcitation down to the passage through a conical intersection, a funnel connecting different electronic states. In this work, we analyze a full in silico photochemical experiment, from the explicit electronic excitation by a laser pul...
Article
Photoactive proteins typically rely on structural changes in a small chromophore to initiate a biological response. While these changes often involve isomerization as the "primary step", preceding this is an ultrafast relaxation of the molecular framework caused by the sudden change in electronic structure upon photoexcitation. Here, we capture thi...
Article
Progression of computational resources towards exascale computing makes possible simulations of unprecedented accuracy and complexity in the fields of materials and molecular modelling (MMM), allowing high fidelity in silico experiments on complex materials of real technological interest. However, this presents demanding challenges for the software...
Article
Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.
Article
Full-text available
Control of the delayed emission of organic compounds is an important factor in the development of new display technology and for the emerging use of organic emitters in sensing and fluorescence microscopy. In particular, there is a need to understand how the phenomena of room-temperature phosphorescence and thermally activated delayed fluorescence...
Article
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Characterizing the photochemical reactivity of transient volatile organic compounds (VOCs) in our atmosphere begins with a proper understanding of their abilities to absorb sunlight. Unfortunately, the photoabsorption cross-sections for a large number of transient VOCs remain unavailable experimentally due to their short lifetime or high reactivity...
Article
Full-text available
Full multiple spawning (FMS) offers an exciting framework for the development of strategies to simulate the excited-state dynamics of molecular systems. FMS proposes to depict the dynamics of nuclear wavepackets by using a growing set of traveling multidimensional Gaussian functions called trajectory basis functions (TBFs). Perhaps the most recogni...
Article
Full-text available
We present a detailed study of the decoherence correction to surface hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and the same electronic structure method are used as a reference for three molecules: ethylene, the methaniminium cation, and fulv...
Article
Full-text available
Ab initio multiple spawning (AIMS) offers a reliable strategy to describe the excited-state dynamics and nonadiabatic processes of molecular systems. AIMS represents nuclear wavefunctions as linear combinations of traveling, coupled Gaussians called trajectory basis functions (TBFs) and uses a spawning algorithm to increase as needed the size of th...
Article
Full-text available
Several electronic-structure methods are available to study the photochemistry and photophysics of organic molecules. Among them, ADC(2) stands as a sweet spot between computational efficiency and accuracy. As a result, ADC(2) has recently seen its number of applications booming, in particular to unravel the deactivation pathways and photodynamics...
Article
Full-text available
We propose and test an extension of the energy-grained master equation (EGME) for treating nonadiabatic (NA) hopping between different potential energy surfaces, which enables us to model the competition between stepwise collisional relaxation and kinetic processes which transfer population between different electronic states of the same spin symme...
Preprint
Full-text available
We present a detailed study of the decoherence correction to surface-hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and same electronic structure method are used as a reference for three molecules: ethylene, methaniminium cation, and fulvene, for...
Article
Full-text available
Ab Initio Multiple Spawning (AIMS) simulates the excited-state dynamics of molecular systems by representing nuclear wavepackets in a basis of coupled traveling Gaussian functions, called trajectory basis functions (TBFs). New TBFs are spawned when nuclear wavepackets enter regions of strong nonadiabaticity, permitting the description of non-Born–O...
Preprint
Full-text available
Here we outline and test an extension of the energy grained master equation (EGME) for treating nonadiabatic (NA) hopping between different potential energy surfaces, which enables us to model the competition between stepwise collisional relaxation and kinetic processes which transfer population between different potential energy surfaces of the sa...
Article
Full-text available
Ideal emitters for organic light-emitting diodes (OLEDs) are capable of efficiently harvesting non-emissive triplet states, have high colour purity, and possess high photoluminescence quantum yields (PLQYs). Maintaining colour purity and PLQY is particularly challenging for multi-carbazole thermally activated delayed fluorescence (TADF) materials t...
Chapter
This Chapter describes the method for non‐adiabatic quantum molecular dynamics called Full Multiple Spawning. The Full Multiple Spawning framework proposes to portray nuclear wave functions by linear combinations of classically‐traveling multi‐dimensional Gaussian functions, called trajectory basis functions. The number of trajectory basis function...
Article
Full-text available
Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we appl...
Article
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We present a series of standardized molecular tests for nonadiabatic dynamics, reminiscent of the one-dimensional Tully models proposed in 1990.
Article
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Ab initio multiple spawning provides a powerful and accurate way of describing the excited-state dynamics of molecular systems, whose strength resides in the proper description of coherence effects during nonadiabatic processes thanks to the coupling of trajectory basis functions. However, the simultaneous propagation of a large number of trajector...
Article
Full-text available
Volatile organic compounds (VOC) are ubiquitous atmospheric molecules that generate a complex network of chemical reactions in the troposphere, often triggered by the absorption of sunlight. Understanding the VOC composition of the atmosphere relies on our ability to characterize all of their possible reaction pathways. When considering reactions o...
Article
Full-text available
Charge transfer in organic fluorophores is a fundamental photophysical process that can be either beneficial, e.g., facilitating thermally activated delayed fluorescence, or detrimental, e.g., mediating emission quenching. N-Alkylation is shown to provide straightforward synthetic control of the charge transfer, emission energy and quantum yield of...
Article
Full-text available
Understanding the connection between the motion of the nuclei in a molecule and the rearrangement of its electrons lies at the heart of chemistry. While many experimental methods have been developed to probe either the electronic or the nuclear structure on the timescale of atomic motion, very few have been able to capture both these changes in con...
Preprint
Charge transfer in organic fluorophores is a fundamental photophysical process that can be either beneficial, e.g., facilitating thermally activated delayed fluorescence, or detrimetnal, e.g., mediating emission quenching. N -Alkylation is shown to provide straightforward synthetic control of the charge transfer, emission energy and quantum yield o...
Preprint
Photo-induced isomerization reactions, including ring-opening reactions, lie at the heart of many processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics unfolding on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degre...
Article
The reaction of nitrous oxide (N2O) with N-heterocyclic olefins (NHOs) results in cleavage of the N-O bond and formation of azo-bridged NHO dimers. The latter represent very electron-rich compounds with a low ionization energy. Cyclic voltammetry studies show that the dimers can be classified as new organic super-electron-donors, with a reducing po...
Article
Full-text available
Simulating the dynamics of a molecule initiated in an excited electronic state constitutes a rather challenging task for theoretical and computational chemistry, as such dynamics leads to a strong coupling between nuclear motion and electronic states, that is, a breakdown of the Born–Oppenheimer approximation. This New Views article proposes a brie...
Article
The cover image is based on the Overview Different flavors of nonadiabatic molecular dynamics, by Federica Agostini and Basile F. E. Curchod. DOI: 10.1002/wcms1417 Abstract The cover image is based on the Overview Different flavors of nonadiabatic molecular dynamics, by Federica Agostini and Basile F. E. Curchod. DOI: 10.1002/wcms1417
Article
Trajectory surface hopping and ab initio multiple spawning are two commonly employed methods for simulating the excited-state dynamics of molecules. Trajectory surface hopping portrays the dynamics of nuclear wavepackets by a swarm of independent classical trajectories, which can hop between electronic states. Ab initio multiple spawning, on the ot...
Article
The Born‐Oppenheimer approximation constitutes a cornerstone of our understanding of molecules and their reactivity, partly because it introduces a somewhat simplified representation of the molecular wavefunction. However, when a molecule absorbs light containing enough energy to trigger an electronic transition, the simplistic nature of the molecu...
Article
We propose a pump-dump control scheme using sub-10 fs pulses to enhance the photochemical formation of the three-membered C–S–O ring oxathiirane from the parent H2CSO sulfine molecule. The ultrashort nature of the pulses is essential to promptly alter the photoinduced dynamics, e.g., while a bond is elongating, which is key to selectively form the...
Article
Full-text available
An understanding of the initial photoexcited states of DNA is essential to unravelling deleterious photoinduced chemical reactions and the intrinsic ultrafast photoprotection of the genetic code for all life. In our combined experimental and theoretical study, we have elucidated the primary non-radiative relaxation dynamics of a model nucleotide of...
Article
We address the problem of electron-nuclear entanglement in time-dependent molecular wavefunctions, key quantities of quantum nonadiabatic molecular dynamics. The most natural way of tackling this question consists in comparing the nonadiabatic dynamics obtained from time-dependent self-consistent field and the exact factorization of the time-depend...
Article
In this work, we investigate the factors influencing the shape of the low-energy tail of the absorption spectrum of a homoleptic biscyclometalated ruthenium complex with terdentate ligands [Rees et al., Inorganic Chemistry, 2017, 56, 9903] by combining an advanced theoretical strategy and the synthesis of an analogous Osmium complex. The theoretica...
Article
Frequency-resolved (2D) photoelectron (PE) spectra of the anionic clusters (C6F6) n-, for n = 1-5, and time-resolved PE spectra of I-C6F6 are presented using a newly built instrument and supported by electronic structure calculations. From the 2D PE spectra, the vertical detachment energy (VDE) of C6F6- was measured to be 1.60 ± 0.01 eV, and the ad...
Article
Electric fields can tailor molecular potential energy surfaces by interaction with the electronic state-dependent molecular dipole moment. Recent developments in optics have enabled the creation of ultra-short few-cycle optical pulses with precise control of the carrier envelope phase (CEP) that determines the offset of the maxima in the field and...
Article
Azoimidazolium dyes were used as precursors for mesoionic carbene ligands (Azo‐MICs). The properties of these ligands were examined by synthesizing RhI, AuI, and PdII complexes. Experimental (NMR, IR) and theoretical investigations show that Azo‐MICs are potent σ‐donor ligands. Yet, they feature a small singlet‐triplet gap and very low‐lying LUMO l...
Article
Azoimidazolium dyes were used as precursors for mesoionic carbene ligands (Azo‐MICs). The properties of these ligands were examined by synthesizing RhI, AuI, and PdII complexes. Experimental (NMR, IR) and theoretical investigations show that Azo‐MICs are potent σ‐donor ligands. Yet, they feature a small singlet‐triplet gap and very low‐lying LUMO l...
Article
Full-text available
Capturing nuclear dynamics through conical intersections is pivotal to understand the fate of photoexcited molecules. The concept of a conical intersection, however, belongs to a specific definition of the electronic states, within a Born–Huang representation of the molecular wavefunction. How would these ultrafast funneling processes be translated...
Article
Upon photoexcitation by a short light pulse, molecules can reach regions of the configuration space characterized by strong nonadiabaticity, where the motion of the nuclei is strongly coupled to the motion of the electrons. The subtle interplay between the nuclear and electronic degrees of freedom in such situations is rather challenging to capture...
Article
Photodynamical simulations are increasingly used for exploring photochemical mechanisms and interpreting laser experiments. The vast majority of ab initio excited-state simulations are performed within semiclassical, trajectory-based approaches. Apart from the underlying electronic-structure theory, the reliability of the simulations is controlled...
Article
The Born–Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamic...
Article
Full-text available
Full Multiple Spawning offers an in principle exact framework for excited-state dynamics, where nuclear wavefunctions in different electronic states are represented by a set of coupled trajectory basis functions that follow classical trajectories. The couplings between trajectory basis functions can be approximated to treat molecular systems, leadi...
Article
Full-text available
Ultrafast proton migration and isomerization are key processes for acetylene and its ions. However, the mechanism for ultrafast isomerization of acetylene [HCCH]²⁺ to vinylidene [H2CC]²⁺ dication remains nebulous. Theoretical studies show a large potential barrier ( > 2 eV) for isomerization on low-lying dicationic states, implying picosecond or lo...
Article
Ozonolysis, the mechanism by which alkenes are oxidized by ozone in the atmosphere, produces a diverse family of oxidants known as Criegee intermediates (CIs). Using a combination of newly acquired laboratory data and global atmospheric chemistry and transport modelling, we find that the reaction of CIs with alcohols – a reaction that was originall...
Article
Full-text available
The calculation of accurate excitation energies using ab-initio electronic structure methods such as standard EOM-CCSD has been cost prohibitive for large systems. In this work, we use a simple projector-based embedding scheme to calculate the EOM-CCSD excitation energies of acrolein solvated in water molecules modelled using DFT. We demonstrate th...
Article
Ultrafast, reversible intersystem crossing (ISC) is reported under ambient conditions for the ground electronic state of the pentacoordinate cobalt nitrosyl complexes, [CoX₂(NO)(PMePh₂)₂] (X = Cl, Br), in solution. ISCs on such short timescales are more typically observed in electronically excited states reached by absorption of ultraviolet or visi...
Article
Ultrafast, reversible intersystem crossing (ISC) is reported under ambient conditions for the ground electronic state of the pentacoordinate cobalt nitrosyl complexes, [CoX₂(NO)(PMePh₂)₂] (X = Cl, Br), in solution. ISCs on such short timescales are more typically observed in electronically excited states reached by absorption of ultraviolet or visi...
Article
A series of six homoleptic bis-cyclometalated ruthenium complexes, Ru(N^N^C)2, is reported where N^N^C is a 6-(2,4-difluoro-3-R(3)-phenyl)-4-R(2)-4'-R(1)-2,2'-bipyridine with R(3) = -H or -CF3 and R(2) and R(1) = -COOEt or -CF3. An effective synthesis of the ligands and the complexes is described. The UV-visible absorption studies demonstrate that...
Article
The ultrafast decay dynamics of 4-(N,N-dimethylamino)benzonitrile (DMABN) following photoexcitation was studied with the ab initio multiple spawning (AIMS) method, combined with GPU-accelerated linear-response time-dependent density functional theory (LR-TDDFT). We validate the LR-TDDFT method for this case and then present a detailed analysis of t...
Article
Attoscience is an emerging field where attosecond pulses or few cycle IR pulses are used to pump and probe the correlated electron-nuclear motion of molecules. We present the trajectory-guided eXternal Field Ab Initio Multiple Spawning (XFAIMS) method that models such experiments “on-the-fly,” from laser pulse excitation to fragmentation or nonadia...
Article
A fundamental tenet of statistical rate theories (such as transition state theory and RRKM) is the rapidity of vibrational relaxation. Excited-state reactions happen quite quickly (sub-picosecond) and thus can exhibit nonstatistical behavior. However, it is often thought that any diversity of photoproducts results from different conical intersectio...
Article
A fundamental tenet of statistical rate theories (such as transition state theory and RRKM) is the rapidity of vibrational relaxation. Excited-state reactions happen quite quickly (sub-picosecond) and thus can exhibit nonstatistical behavior. However, it is often thought that any diversity of photoproducts results from different conical intersectio...
Article
Excited-state molecular dynamics is essential to the study of photochemical reactions, which occur under nonequilibrium conditions. However, the computational cost of such simulations has often dictated compromises between accuracy and efficiency. The need for an accurate description of both the molecular electronic structure and nuclear dynamics h...
Preprint
Full-text available
Experimental evidence has pointed toward the existence of ultrafast proton migration and isomerization as a key process for acetylene and its ions, however the actual mechanism for ultrafast isomerization of the acetylene [HCCH]2+ to vinylidene [H2CC]2+ dication remains nebulous. Theoretical studies show a high potential barrier of over 2 eV [J. Ch...