Excited-state Calculations Research Articles

Influence of pseudo-Jahn-Teller activity on the singlet-triplet gap of azaphenalenes.

We analyze the possibility of symmetry-lowering induced by pseudo-Jahn-Teller interactions in six previously studied azaphenalenes that are known to have their first excited singlet state (S1) lower in energy than the triplet state (T1). The primary aim of this study is to explore whether Hund's rule violation is observed in these molecules when their structures are distorted from C2v or D3h point group symmetries by vibronic coupling. Along two interatomic distances connecting these point groups to their subgroups Cs or C3h, we relaxed the other internal degrees of freedom and calculated two-dimensional potential energy subsurfaces. The many-body perturbation theory (MP2) suggests that the high-symmetry structures are the energy minima for all six systems. However, single-point energy calculations using the coupled-cluster method (CCSD(T)) indicate symmetry lowering in four cases. The singlet-triplet energy gap plotted on the potential energy surface also shows variations when deviating from high-symmetry structures. A full geometry optimization at the CCSD(T) level with the cc-pVTZ basis set reveals that the D3h structure of cyclazine (1AP) is a saddle point, connecting two equivalent minima of C3h symmetry undergoing rapid automerization. The combined effects of symmetry lowering and high-level corrections result in a nearly zero singlet-triplet gap for the C3h structure of cyclazine. Azaphenalenes containing nitrogen atoms at electron-deficient sites - 2AP, 3AP, and 4AP - exhibit more pronounced in-plane structural distortion; the effect is captured by the long-range exchange-interaction corrected DFT method, ωB97XD. Excited state calculations of these systems indicate that in their low-symmetry energy minima, T1 is indeed lower in energy than S1, upholding the validity of Hund's rule. Jahn-Teller analysis predicts the symmetries of the in-plane distortion vibrational modes as or B2: C2v → Cs agreeing with the vibrational frequencies of the saddle-points.

Using ground state and excited state density functional theory to decipher 3d dopant defects in GaN

Using ground state density functional theory (DFT) and implementing an occupation-constrained DFT (occ-DFT) for self-consistent excited state calculations, we decipher the electronic structure of the Mn dopant and other 3ddefects in GaN across the band gap. Our analysis, validated with broad agreement with defect levels (ground-state calculations) and photoluminescence data (excited-state calculations), mandates reinterpretation and reassignment of 3ddefect data in GaN. The MnGadefect is determined to span stable charge states from (1-) inn-type GaN through (2+) inp-type GaN. The Mn(2+) is predicted to be ad2ground state spin triplet defect with a singlet excited state, isoelectronic with the defect associated with the 1.19 eV photoluminescence inn-type GaN. The combined analysis of defect levels and excited states invites reassessment of alld2-capable dopants in GaN. We demonstrate that the 1.19 eV defect, a candidate defect for optically controlled quantum applications, cannot be the Cr(1+) assumed in literature and instead must be the V(0). The combined ground-state/excited-state DFT analysis is shown to be able to chemically fingerprint defects.

Storehouse of Peculiar Supramolecular Architecture: Probing the Charge-Transfer Phenomenon and Effect of Altering the pH in a Meta-Oriented Single Donor-Double Acceptor Fluorophore.

The investigation of excited-state intramolecular charge transfer (ESICT) has been a fascinating area of research. Although the ESICT events have been studied mostly for para-disubstituted donor-acceptor type molecules, the meta-oriented donor-acceptor type molecules have also shown tremendous potential as ESICT active molecules. In the current work, a small fluorescent probe diethyl 5-amino isophthalate (DE-5A-IPA) was investigated as a potential model to investigate ESICT events in the solution as well as solid phase. DE-5A-IPA was synthesized easily starting from commercially available 5-amino isophthalic acid in excellent yield. In the solid state, differing extents of CH···π-type binding led to formation of fully planar and puckered "cyclobutane" mimic supramolecular architecture, as evidenced from the crystal structure analysis. In addition, the single crystal structure of DE-5A-IPA shows that the donor (-NH2) and acceptor (-CO2Et) are situated in the same plane, thereby assuring the prerequisites of a through-space charge transfer. DE-5A-IPA undergoes noticeable Stokes shift (in cm-1) when the polarity of the medium was changed (4820 cm-1 in hexane; 9375 cm-1 in water). The excited-state dipole moment (μe) was calculated to be 4.0 units higher than the ground-state dipole moment (μg). DE-5A-IPA had an appreciable quantum yield (0.10 ± 0.03 to 0.27 ± 0.04). The ESICT phenomenon was also investigated by ground- and excited-state structural calculations using Gaussian 16 software. The excited-state lifetime measured by the time correlated single photon counting technique was found to vary with the polarity of the solvent, thereby providing further support to the ESICT phenomenon being operative in DE-5A-IPA. Taking advantage of the -NH2 group (which is susceptible to protonation) in DE-5A-IPA, steady state and time-resolved photodynamics were investigated in solutions of varying pH values. Interestingly, the emission quantum yields as well as the emission lifetime increase with an increase in pH value, thereby establishing DE-5A-IPA as a pH-sensitive probe. The current findings shall boost the understanding of meta-oriented ESICT enabled compounds in terms of their excited-state photophysics.

Spectral densities, structured noise and ensemble averaging within open quantum dynamics.

Although recent advances in simulating open quantum systems have led to significant progress, the applicability of numerically exact methods is still restricted to rather small systems. Hence, more approximate methods remain relevant due to their computational efficiency, enabling simulations of larger systems over extended timescales. In this study, we present advances for one such method, namely, the numerical integration of Schrödinger equation (NISE). First, we introduce a modified ensemble-averaging procedure that improves the long-time behavior of the thermalized variant of the NISE scheme, termed thermalized NISE. Second, we demonstrate how to use the NISE in conjunction with (highly) structured spectral densities by utilizing a noise generating algorithm for arbitrary structured noise. This algorithm also serves as a tool for establishing best practices in determining spectral densities from excited state calculations along molecular dynamics or quantum mechanics/molecular mechanics trajectories. Finally, we assess the ability of the NISE approach to calculate absorption spectra and demonstrate the utility of the proposed modifications by determining population dynamics.

Subspace-Search Quantum Imaginary Time Evolution for Excited State Computations.

Quantum systems in excited states are attracting significant interest with the advent of noisy intermediate-scale quantum (NISQ) devices. While ground states of small molecular systems are typically explored using hybrid variational algorithms like the variational quantum eigensolver (VQE), the study of excited states has received much less attention, partly due to the absence of efficient algorithms. In this work, we introduce the subspace search quantum imaginary time evolution (SSQITE) method, which calculates excited states using quantum devices by integrating key elements of the subspace search variational quantum eigensolver (SSVQE) and the variational quantum imaginary time evolution (VarQITE) method. The effectiveness of SSQITE is demonstrated through calculations of low-lying excited states of benchmark model systems including H2 and LiH molecules. A toy Hamiltonian is also employed to demonstrate that the robustness of VarQITE in avoiding local minima extends to its use in excited state algorithms. With this robustness in avoiding local minima, SSQITE shows promise for advancing quantum computations of excited states across a wide range of applications.

Accurate determination of excitation energy: An equation-of-motion approach over a bi-exponential coupled cluster theory.

The calculation of molecular excited states is critically important to decipher a plethora of molecular properties. In this paper, we develop an equation of motion formalism on top of a bi-exponentially parameterized ground state wavefunction toward the determination of excited states. While the ground state bi-exponential parameterization ensures an accurate description of the wavefunction through the inclusion of high-rank correlation effects, the excited state is parameterized by a novel linear response operator with an effective excitation rank beyond two. To treat the ground and excited states in the same footings, in addition to the conventional one- and two-body response operators, we introduced certain two-body "generalized" response operators with an effective excitation rank of one. We introduce a projective formulation for determining the perturbed amplitudes for the set of "generalized" operators. Our formulation entails a significantly small number of unknown parameters and is shown to be highly accurate compared to allied methods for several difficult chemical systems.

Tautomer-Selective Fluorescence Spectroscopy of Oxyluciferin Anions.

Bioluminescence in fireflies and related insects arises as emission from the fluorophore oxyluciferin, yet the color of the emission in these insects can range from red to green. The chromophore's microenvironment or multiple tautomeric forms may be responsible for the color tuning; however, these effects are difficult to separate in condensed phases. To investigate the role of oxyluciferin tautomerization in the color tuning mechanism, gas-phase spectroscopy eliminates solvent effects and allows us to study the fluorescence from individual tautomers. Using a home-built mass-spectrometry setup with a cylindrical ion trap cooled with liquid nitrogen, we measure fluorescence from the enol-locked form of oxyluciferin in the gas phase and characterize the photophysics of both keto and enol forms. At 100 K, the enol-locked form has an emission maximum of 564 ± 1 nm, coinciding with a previously reported assignment in oxyluciferin. We measure the absorption spectrum and find a maximum at 560.5 ± 0.5 nm, which implies a Stokes shift of 110 cm-1. The absorption spectrum is compared to Franck-Condon simulated spectra that identify one dominant vibrational mode in the transition. Additionally, we ultimately separated the emission by the enol and keto forms present in the trap by selectively exciting each form. We demonstrate that fluorescence measured close to the 0-0 transition limits the reheating of the ions, thereby providing the coldest ions and therefore the narrowest emission spectra. These experimental data are also crucial benchmarks for computational studies, offering actual emission spectra in the gas phase for both tautomeric forms. Thus, our findings serve as essential reference points for excited-state calculations aimed at understanding the color tuning mechanism of bioluminescence computationally.

2-(1,1-Dicyanomethylene)rhodanine-Functionalized Oligothiophenes: A Structure-Property Investigation of Z/E Photoisomerization Behavior.

A series of oligothiophenes singly and doubly functionalized with dicyanorhodanine (RCN) units have been investigated to understand their Z/E photoisomerization behavior upon structural modulation. Monotopic RCN target molecules (1-Z-9-Z) were designed to observe the consequences of π-conjugation, solubilizing group substitution, and formylation of the thiophene units. In all cases, the Z isomer is obtained from synthesis as the thermodynamically stable isomer, whereas the E isomer is achieved through selective irradiation (including red light, λirr = 628 nm) as a Z/E mixture in solution. For the quarterthiophene entries, photoisomerization is inhibited, with photoirradiation resulting only in degradation. The result comports with concentration-dependent studies, which show that increasing π-conjugation results in greater aggregation and muted Z/E photoisomerization. Ditopic RCN targets (10-ZZ-12-ZZ), mimicking acceptor-donor-acceptor (A-D-A) oligomers relevant to OPV materials, also show evidence of photoisomerization in solution, with formation of Z,Z/Z,E mixtures at the photostationary state (PSS). Complementary ground- and excited-state DFT calculations show excellent agreement with the experimental findings. This comprehensive structure-property analysis is expected to both guide and caution the functional materials community with respect to the usage of photoisomerizable RCN-oligothiophenes for optoelectronic applications.

Ab Initio Multiple Spawning Nonadiabatic Dynamics with Different CASPT2 Flavors: A Fully Open-Source PySpawn/OpenMolcas Interface.

We introduce an interface between PySpawn, a simulation package to run ab initio multiple spawning (AIMS) nonadiabatic dynamics, and OpenMolcas, a software package to perform multiconfigurational perturbations theory (CASPT2) electronic structure calculations. Our interface allows us to exploit all the functionalities of the two codes: the modular and efficient Python implementation of the AIMS algorithm and the extensive analysis tools offered by PySpawn, with the cutting-edge implementation of CASPT2 equations in OpenMolcas, including the recently introduced analytical gradients and different flavors. Both are fully open-source and free of charge, making the following implementation unique in the current plethora of software for nonadiabatic dynamics. This represents an important step toward a wider application of AIMS-based nonadiabatic dynamics combined with high-accuracy excited-state calculations. The importance and the need for such an implementation are demonstrated by application to the ultrafast relaxation of fulvene from S1 to S0, which is drastically affected by the potential energy surface on which the nuclear wavepacket is propagated. Additionally, the decay is influenced by the CASPT2 flavor adopted, posing interesting questions in the choice of one over the other and opening the door to deeper studies on the effect of CASPT2 formulations in nonadiabatic dynamics.

Quantum Chemistry Dataset with Ground- and Excited-state Properties of 450 Kilo Molecules

Due to rapid advancements in deep learning techniques, the demand for large-volume high-quality datasets grows significantly in chemical research. We developed a quantum-chemistry database that includes 443,106 small organic molecules with sizes up to 10 heavy atoms including C, N, O, and F. Ground-state geometry optimizations and frequency calculations of all compounds were performed at the B3LYP/6-31G* level with the BJD3 dispersion correction, while the excited-state single-point calculations were conducted at the ωB97X-D/6-31G* level. Totally twenty-seven molecular properties, such as geometric, thermodynamic, electronic and energetic properties, were gathered from these calculations. Meanwhile, we also established a comprehensive protocol for the construction of a high-volume quantum-chemistry dataset. Our QCDGE (Quantum Chemistry Dataset with Ground- and Excited-State Properties) dataset contains a substantial volume of data, exhibits high chemical diversity, and most importantly includes excited-state information. This dataset, along with its construction protocol, is expected to have a significant impact on the broad applications of machine learning studies across different fields of chemistry, especially in the area of excited-state research.

Combined Multireference-Multiscale Approach to the Description of Photosynthetic Reaction Centers.

A first-principles description of the primary photochemical processes that drive photosynthesis and sustain life on our planet remains one of the grand challenges of modern science. Recent research established that explicit incorporation of protein electrostatics in excited-state calculations of photosynthetic pigments, achieved for example with quantum-mechanics/molecular-mechanics (QM/MM) approaches, is essential for a meaningful description of the properties and function of pigment-protein complexes. Although time-dependent density functional theory has been used productively so far in QM/MM approaches for the study of such systems, this methodology has limitations. Here we pursue for the first time a QM/MM description of the reaction center in the principal enzyme of oxygenic photosynthesis, Photosystem II, using multireference wave function theory for the high-level QM region. We identify best practices and establish guidelines regarding the rational choice of active space and appropriate state-averaging for the efficient and reliable use of complete active space self-consistent field (CASSCF) and the N-electron valence state perturbation theory (NEVPT2) in the prediction of low-lying excited states of chlorophyll and pheophytin pigments. Given that the Gouterman orbitals are inadequate as a minimal active space, we define specific minimal and extended active spaces for the NEVPT2 description of electronic states that fall within the Q and B bands. Subsequently, we apply our multireference-QM/MM protocol to the description of all pigments in the reaction center of Photosystem II. The calculations reproduce the electrochromic shifts induced by the protein matrix and the ordering of site energies consistent with the identity of the primary donor (ChlD1) and the experimentally known asymmetric and directional electron transfer. The optimized protocol sets the stage for future multireference treatments of multiple pigments, and hence for multireference studies of charge separation, while it is transferable to the study of any photoactive embedded tetrapyrrole system.

Identification of a Weak Interaction between the Spin-Only 4f-Electronic System of Trivalent Gd Ion and a Photoexcited Cyclic π Electronic System.

An electronic interaction between the spin-only 4f-electronic system and the photoexcited π cyclic system has been identified in the anionic bis(phthalocyaninato)gadolinium(III) complex [Pc2Gd]- by using variable-temperature variable-magnetic-field magnetic circular dichroism (VTVH MCD). Two positive MCD A-term patterns, corresponding to the QH and QL absorption bands, were observed to increase in intensity as the temperature decreased, indicating a ferromagnetic-type interaction between spin angular momentum S of the 4f system and orbital angular momentum L of the photoexcited π system. A theoretical model incorporating the S-L interaction constant CSL was fitted to the VTVH MCD spectra, confirming the presence of a weak interaction, whose intensity was determined as CSL = 0.27 cm-1 for QL and CSL = 0.02 cm-1 for QH. Ab initio calculations using the RASSCF and RASSI methods revealed that the inclusion of the excited state calculations with the spin multiplicity (2S + 1) of 6 was crucial for assigning ΔSL and CSL values. This underscores the essential role of the 6PJ term in accurately modeling the S-L interaction in [Pc2Gd]-.

Coupling molecular density functional theory with converged selected configuration interaction methods to study excited states in aqueous solution.

This paper presents the first implementation of a coupling between advanced wavefunction theories and molecular density functional theory (MDFT). This method enables the modeling of solvent effect into quantum mechanical (QM) calculations by incorporating an electrostatic potential generated by solvent charges into the electronic Hamiltonian. Solvent charges are deduced from the spatially and angularly dependent solvent particle density. Such a density is obtained through the minimization of the functional associated with the molecular mechanics (MM) Hamiltonian describing the interaction between the fluid particles. The introduced QM/MDFT framework belongs to QM/MM family of methods, but its originality lies in the use of MDFT as the MM solver, offering two main advantages. First, its functional formulation makes it competitive with respect to sampling-based molecular mechanics. Second, it preserves a molecular-level description lost in macroscopic continuum approaches. The excited state properties of water and formaldehyde molecules solvated into water have been computed at the selected configuration interaction (SCI) level. The excitation energies and dipole moments have been compared with experimental data and previous theoretical work. A key finding is that using the Hartree-Fock method to describe the solute allows for predicting the solvent charge around the ground state with sufficient precision for the subsequent SCI calculations of excited states. This significantly reduces the computational cost of the described procedure, paving the way for the study of more complex molecules.

Construction of Highly Accurate Machine Learning Potential Energy Surfaces for Excited-State Dynamics Simulations Based on Low-Level Data Sets.

Machine learning is capable of effectively predicting the potential energies of molecules in the presence of high-quality data sets. Its application in the construction of ground- and excited-state potential energy surfaces is attractive to accelerate nonadiabatic molecular dynamics simulations of photochemical reactions. Because of the huge computational cost of excited-state electronic structure calculations, the construction of a high-quality data set becomes a bottleneck. In the present work, we first built two data sets. One was obtained from surface hopping dynamics simulations at the semiempirical OM2/MRCI level. Another was extracted from the dynamics trajectories at the CASSCF level, which was reported previously. The ground- and excited-state potential energy surfaces of ethylene-bridged azobenzene at the CASSCF computational level were constructed based on the former low-level data set. Although non-neural network machine learning methods can achieve good or modest performance during the training process, only neural network models provide reliable predictions on the latter external test data set. The BPNN and SchNet combined with the Δ-ML scheme and the force term in the loss functions are recommended for dynamics simulations. Then, we performed excited-state dynamics simulations of the photoisomerization of ethylene-bridged azobenzene on machine learning potential energy surfaces. Compared with the lifetimes of the first excited state (S1) estimated at different computational levels, our results on the E isomer are in good agreement with the high-level estimation. However, the overestimation of the Z isomer is unimproved. It suggests that smaller errors during the training process do not necessarily translate to more accurate predictions on high-level potential energies or better performance on nonadiabatic dynamics simulations, at least in the present case.

Fighting Noise with Noise: A Stochastic Projective Quantum Eigensolver.

In the current noisy intermediate scale quantum era of quantum computation, available hardware is severely limited by both qubit count and noise levels, precluding the application of many current hybrid quantum-classical algorithms to nontrivial quantum chemistry problems. In this paper we propose applying some of the fundamental ideas of conventional Quantum Monte Carlo algorithms─stochastic sampling of both the wave function and the Hamiltonian─to quantum algorithms in order to significantly decrease quantum resource costs. In the context of an imaginary-time propagation based projective quantum eigensolver, we present a novel approach to estimating physical observables which can lead to an order of magnitude reduction in the required sampling of the quantum state to converge the ground state energy of a system relative to current state-of-the-art eigensolvers. The method can be equally applied to excited-state calculations and, combined with stochastic approximations of the system Hamiltonian, provides a promising near-term approach to Hamiltonian simulation for general chemistry on quantum devices.

β decay of the ground state and of a low-lying isomer in Bi216

A detailed β-decay study of the low- and high-spin states in Bi216 has been performed at the ISOLDE Decay Station at the CERN-ISOLDE facility. In total, 48 new levels and 83 new transitions in the β-decay daughter Po216 were identified. Shell-model calculations for excited states in Bi216 and Po216 were performed using the H208 and the modified Kuo-Herling particle effective interactions. Based on the experimental observations and the shell-model calculations, the most likely spin and parity assignments for the β-decaying states in Bi216 are (3−) and (8−), respectively. Published by the American Physical Society 2024

Excitation configuration analysis for divide-and-conquer excited-state calculation method using dynamical polarizability.

The authors previously developed a divide-and-conquer (DC)-based non-local excited-state calculation method for large systems using dynamical polarizability [Nakai and Yoshikawa, J. Chem. Phys. 146, 124123 (2017)]. This method evaluates the excitation energies and oscillator strengths using information on the dynamical polarizability poles. This article proposes a novel analysis of the previously developed method to obtain further configuration information on excited states, including excitation and de-excitation coefficients of each excitation configuration. Numerical applications to simple molecules, such as ethylene, hydrogen molecule, ammonia, and pyridazine, confirmed that the proposed analysis could accurately reproduce the excitation and de-excitation coefficients. The combination with the DC scheme enables both the local and non-local excited states of large systems with an excited nature to be treated.

Multireference Ab Initio Calculations on Excited Electronic States of Carbazole-Based Organic Compounds for Thermally Activated Delayed Fluorescence.

The emerging technology of organic light-emitting diodes takes advantage of the thermally activated delayed fluorescence (TADF) mechanism for improved efficiency. Carbazole-based organic molecules are suitable for TADF emission because of charge transfer excitations between the electron-donor carbazole and an electron-acceptor unit. Computational design of new TADF molecules with the desired properties is challenging because charge-transfer excitations cannot be predicted accurately by time-dependent density functional theory. Four groups of carbazole-based donor-acceptor molecules have been studied using multireference ab initio methods to understand the nature of excited electronic states. The state-averaged complete active space self-consistent field (SA-CASSCF) and the N-electron valence state perturbation theory (NEVPT2) were used to calculate energies and oscillator strengths for multiple excited electronic states. The number of active electrons and orbitals and the number of excited states included in state-averaged CASSCF were selected such that the accuracy of ab initio predictions could be improved systematically. The procedure introduced here for the calculation of multiple excited electronic states of TADF candidates can be used to accelerate the computational search for efficient TADF materials.

Axial H-Bonding Solvent Controls Inhomogeneous Spectral Broadening, While Peripheral H-Bonding Solvent Controls Vibronic Broadening: Cresyl Violet in Methanol.

The dynamics of the nuclei of both a chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore-solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both chromophore and its condensed-phase environment control many spectral features, including the vibronic and inhomogeneous broadening present in spectral line shapes. For the cresyl violet chromophore in methanol, we here analyze and isolate the effect of specific chromophore-solvent interactions on simulated spectral densities, reorganization energies, and linear absorption spectra. Employing both force field and ab initio molecular dynamics trajectories along with the inclusion of only certain solvent molecules in the excited-state calculations, we determine that the methanol molecules axial to the chromophore are responsible for the majority of inhomogeneous broadening, with a single methanol molecule that forms an axial hydrogen bond dominating the response. The strong peripheral hydrogen bonds do not contribute to spectral broadening, as they are very stable throughout the dynamics and do not lead to increased energy-gap fluctuations. We also find that treating the strong peripheral hydrogen bonds as molecular mechanical point charges during the molecular dynamics simulation underestimates the vibronic coupling. Including these peripheral hydrogen bonding methanol molecules in the quantum-mechanical region in a geometry optimization increases the vibronic coupling, suggesting that a more advanced treatment of these strongly interacting solvent molecules during the molecular dynamics trajectory may be necessary to capture the full vibronic spectral broadening.

Visible and Red Light-Triggered Anticancer Profile of a Ferrocene-Re(I)-Tricarbonyl Conjugate: Experimental and Theoretical Studies.

We have red-shifted the light absorbance property of a Re(I)-tricarbonyl complex via distant conjugation of a ferrocene moiety and developed a novel complex ReFctp, [Re(Fctp)(CO)3Cl], where Fctp = 4'-ferrocenyl-2,2':6',2″-terpyridine. ReFctp showed green to red light absorption ability and blue emission, indicating its potential for photodynamic therapy (PDT) application. The conjugation of ferrocene introduced ferrocene-based transitions, which lie at a higher wavelength within the PDT therapeutic window. The time-dependent density functional theory and excited state calculations revealed an efficient intersystem crossing for ReFctp, which is helpful for PDT. ReFctp elicited both PDT type I and type II pathways for reactive oxygen species (ROS) generation and facilitated NADH (1,4-dihydro-nicotinamide adenine dinucleotide) oxidation upon exposure to visible light. Importantly, ReFctp showed effective penetration through the layers of clinically relevant 3D multicellular tumor spheroids and localized primarily in mitochondria (Pearson's correlation coefficient, PCC = 0.65) of A549 cancer cells. ReFctp produced more than 20 times higher phototoxicity (IC50 ∼1.5 μM) by inducing ROS generation and altering mitochondrial membrane potential in A549 cancer cells than the nonferrocene analogue Retp, [Re(CO)3(tp)Cl], where tp = 2,2':6',2″-terpyridine. ReFctp induced apoptotic mode of cell death with a notable photocytotoxicity index (PI, PI = IC50dark/IC50light) and selectivity index (SI, SI = normal cell's IC50dark/cancer cell's IC50light) in the range of 25-33.