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1. Excited-state dynamics of deuterated indigo

   https://doi.org/10.1140/epjd/s10053-023-00744-z  

   Cohen, Trevor; Svadlenak, Nathan; Smith, Charles; Vo, Krystal; Lee, Si-Young; Parejo-Vidal, Ana; Kincaid, Joseph R. A.; Sobolewski, Andrzej L.; Rode, Michal F.; de Vries, Mattanjah S. (September 2023, The European Physical Journal D)

   Abstract Indigo, a rich blue dye, is an incredibly photostable molecule that has survived in ancient art for centuries. It is also unique in that it can undergo both an excited-state hydrogen and proton transfer on the picosecond timescale followed by a ground-state back transfer. Previously, we performed gas phase excited-state lifetime studies on indigo to study these processes in a solvent-free environment, combined with excited-state calculations. We found two decay pathways, a fast sub-nanosecond decay and a slow decay on the order of 10 ns. Calculations of the excited-state potential energy surface found that both hydrogen and proton transfer are nearly isoenergetic separated by a 0.1 eV barrier. To further elucidate these dynamics, we now report a study with deuterated indigo, using resonance-enhanced multi-photon ionization and pump-probe spectroscopy with mass spectrometric isotopomer selection. From new calculations of the excited-state potential energy surface, we find sequential double-proton or hydrogen transfer, whereby the trajectory to the second transfer passes a second barrier and then encounters a conical intersection that leads back to the ground state. We find that deuteration only increases the excited-state lifetimes of the fast decay channel, suggesting tunneling through the first barrier, while the slower channel is not affected and may involve a different intermediate state. Graphical abstract 

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2. Modeling the effect of substituents on the electronically excited states of indole derivatives

   https://doi.org/10.1002/jcc.27502  

   Howe, Jordan; Abou‐Hatab, Salsabil; Matsika, Spiridoula (September 2024, Journal of Computational Chemistry)

   Abstract A proper understanding of excited state properties of indole derivatives can lead to rational design of efficient fluorescent probes. The optically active and excited states of a series of substituted indoles, where a substituent was placed on position four, were calculated using equation of motion coupled cluster and time dependent density functional theory. The results indicate that most substituted indoles have a brighter second excited state corresponding to experimental absorption maxima, but a few with electron withdrawing substituents absorb more on the first excited state. Absorption on the first excited state may increase their fluorescence quantum yield, making them better probes. Electronic structure methods were found to predict the energies of the systems with electron withdrawing substituents more accurately than those with electron donating substituents. The excited states of both states correlated well with electrophilicity, similar to the experimental trends for the absorption maxima. Overall, these computational studies indicate that theory can be used to predict excited state properties of substituted indoles, when the substituent is an electron withdrawing group. 

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3. Fantastical excited state optimized structures and where to find them

   https://doi.org/10.1063/5.0172015  

   Talbot, Justin J; Arias-Martinez, Juan E; Cotton, Stephen J; Head-Gordon, Martin (November 2023, The Journal of Chemical Physics)

   The quantum chemistry community has developed analytic forces for approximate electronic excited states to enable walking on excited state potential energy surfaces (PES). One can thereby computationally characterize excited state minima and saddle points. Always implicit in using this machinery is the fact that an excited state PES only exists within the realm of the Born-Oppenheimer approximation, where the nuclear and electronic degrees of freedom separate. This work demonstrates through ab initio calculations and simple nonadiabatic dynamics that some excited state minimum structures are fantastical: they appear to exist as stable configurations only as a consequence of the PES construct, rather than being physically observable. Each fantastical structure exhibits an unphysically high predicted harmonic frequency and associated force constant. This fact can serve as a valuable diagnostic of when an optimized excited state structure is non-observable. The origin of this phenomenon can be attributed to the coupling between different electronic states. As PESs approach one another, the upper surface can form a minimum that is very close to a near-touching point. The force constant, evaluated at this minimum, relates to the strength of the electronic coupling rather than to any characteristic excited state vibration. Nonadiabatic dynamics results using a Landau-Zener model illustrate that fantastical excited state structures have extremely short lifetimes on the order of a few femtoseconds. Their appearance in a calculation signals the presence of a nearby conical intersection through which the system will rapidly cross to a lower surface. 

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4. Excited-state spin-resonance spectroscopy of V$${}_{{{{{{{{\rm{B}}}}}}}}}^{-}$$ defect centers in hexagonal boron nitride

   https://doi.org/10.1038/s41467-022-30772-z  

   Mathur, Nikhil; Mukherjee, Arunabh; Gao, Xingyu; Luo, Jialun; McCullian, Brendan A.; Li, Tongcang; Vamivakas, A. Nick; Fuchs, Gregory D. (June 2022, Nature Communications)

   Abstract The recently discovered spin-active boron vacancy (V$${}_{{{{{{{{\rm{B}}}}}}}}}^{-}$$ ${}_B^{-}$) defect center in hexagonal boron nitride (hBN) has high contrast optically-detected magnetic resonance (ODMR) at room-temperature, with a spin-triplet ground-state that shows promise as a quantum sensor. Here we report temperature-dependent ODMR spectroscopy to probe spin within the orbital excited-state. Our experiments determine the excited-state spin Hamiltonian, including a room-temperature zero-field splitting of 2.1 GHz and a g-factor similar to that of the ground-state. We confirm that the resonance is associated with spin rotation in the excited-state using pulsed ODMR measurements, and we observe Zeeman-mediated level anti-crossings in both the orbital ground- and excited-state. Our observation of a single set of excited-state spin-triplet resonance from 10 to 300 K is suggestive of symmetry-lowering of the defect system fromD_3htoC_2v. Additionally, the excited-state ODMR has strong temperature dependence of both contrast and transverse anisotropy splitting, enabling promising avenues for quantum sensing. 

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5. Quantum simulation of excited states from parallel contracted quantum eigensolvers

   https://doi.org/10.1088/1367-2630/ad2d1d  

   Benavides-Riveros, Carlos L.; Wang, Yuchen; Warren, Samuel; Mazziotti, David A. (March 2024, New Journal of Physics)

   Abstract Computing excited-state properties of molecules and solids is considered one of the most important near-term applications of quantum computers. While many of the current excited-state quantum algorithms differ in circuit architecture, specific exploitation of quantum advantage, or result quality, one common feature is their rooting in the Schrödinger equation. However, through contracting (or projecting) the eigenvalue equation, more efficient strategies can be designed for near-term quantum devices. Here we demonstrate that when combined with the Rayleigh–Ritz variational principle for mixed quantum states, the ground-state contracted quantum eigensolver (CQE) can be generalized to compute any number of quantum eigenstates simultaneously. We introduce twoexcited-state(anti-Hermitian) CQEs that perform the excited-state calculation while inheriting many of the remarkable features of the original ground-state version of the algorithm, such as its scalability. To showcase our approach, we study several model and chemical Hamiltonians and investigate the performance of different implementations. 

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