Abstract:Mn(I) -diimine carbonyl complexes have shown promise in the development of luminescent CO release materials (photoCORM) for diagnostic and medical applications due to their ability to balance the energy of the low-lying metal-to-ligand charge transfer (MLCT) and metalcentered (MC) states. In this work, the excited state dynamics of [Mn(im)(CO)3(phen)] + (im = imidazole; phen = 1,10-phenanthroline) is investigated by means of wavepacket propagation on the potential energy surfaces associated to the eleven low-… Show more
“…Compared to MC/MR, SR methods feature a considerably lower scaling in the computational cost with regard to the system size, making them more amenable to transition metal complexes. Applications revolve around (closed-shell) low-spin d 6 complexes ,,− and d 10 systems − with one single exception . As a further advantage, SR methods can be considered more “black box” than MC/MR methods as they typically depend on fewer (and less critical) parameters, which makes them more user-friendly.…”
Section: Electronic Structure Methods
For Dynamics Of
Transition Meta...mentioning
This Perspective
describes current computational efforts in the
field of simulating photodynamics of transition metal complexes. We
present the typical workflows and feature the strengths and limitations
of the different contemporary approaches. From electronic structure
methods suitable to describe transition metal complexes to approaches
able to simulate their nuclear dynamics under the effect of light,
we give particular attention to build a bridge between theory and
experiment by critically discussing the different models commonly
adopted in the interpretation of spectroscopic experiments and the
simulation of particular observables. Thereby, we review all the studies
of excited-state dynamics on transition metal complexes, both in gas
phase and in solution from reduced to full dimensionality.
“…Compared to MC/MR, SR methods feature a considerably lower scaling in the computational cost with regard to the system size, making them more amenable to transition metal complexes. Applications revolve around (closed-shell) low-spin d 6 complexes ,,− and d 10 systems − with one single exception . As a further advantage, SR methods can be considered more “black box” than MC/MR methods as they typically depend on fewer (and less critical) parameters, which makes them more user-friendly.…”
Section: Electronic Structure Methods
For Dynamics Of
Transition Meta...mentioning
This Perspective
describes current computational efforts in the
field of simulating photodynamics of transition metal complexes. We
present the typical workflows and feature the strengths and limitations
of the different contemporary approaches. From electronic structure
methods suitable to describe transition metal complexes to approaches
able to simulate their nuclear dynamics under the effect of light,
we give particular attention to build a bridge between theory and
experiment by critically discussing the different models commonly
adopted in the interpretation of spectroscopic experiments and the
simulation of particular observables. Thereby, we review all the studies
of excited-state dynamics on transition metal complexes, both in gas
phase and in solution from reduced to full dimensionality.
“…139,140. This preference is also mirrored in excited state dynamics studies, that mostly rely on hybrid functionals 32,38,[107][108][109][110][111][112][113][114][115][116][117][118][119][120]126,[128][129][130][131] with some exceptions. [121][122][123][124]129 In addition to the general functional dependence, TDDFT is well known to suffer from its inability to describe CT excitations with standard XC functionals.…”
Section: Time-dependent Density Functional Theorymentioning
confidence: 99%
“…Despite these limitations, LVC has become the standard approach to calculate PES in wave-packet dynamics simulations using MCTDH for transition metal complexes 38,91,[106][107][108][109][110][112][113][114][115][116][126][127][128]130 making it possible to include up to 16 nuclear degrees of freedom. 126 One example of MCTDH using 15 degrees of freedom in a heme-CO complex is shown in Figure 5. Among these studies, it is worth to mention that only two include explicitly the excitation by a laser pulse.…”
Section: Vibronic Coupling Modelsmentioning
confidence: 99%
“…One approach thereby is to select normal modes based on the size of their vibronic coupling terms. 110,126,127,171 As large vibronic coupling elements are needed to efficiently transfer population between the electronic states, these coupling modes are necessary to describe the excited-state dynamics. This selection can be extended by adding tuning modes, which are normal modes that are responsible for the largest displacements in the excitedstate dynamics by reaching towards the excited-state minima 38,[113][114][115][116] and the excited-state crossing points.…”
Section: The Choice Of Degrees Of Freedommentioning
confidence: 99%
“…These models have been applied in excited-state dynamics of solvated transition metal complexes parameterized with LVC potentials using both, MCTDH [107][108][109][110][111][112]116,126,128 and AIMD simulations. [117][118][119]132 Although, in principle, there exist stationary studies where also biological environments are approximately modelled with continuum models with very small dielectric constants, such strategy has not been used for dynamics, as it cannot capture the explicit fluctuations of the complex environments.…”
This Perspective describes current computational efforts in the field of simulating photodynamics of transition metal complexes. We present the typical workflows and feature the strengths and limitations of the different contemporary approaches.From electronic structure methods suitable to describe transition metal complexes to approaches able to simulate their nuclear dynamics under the effect of light, we lay particular attention to build a bridge between theory and experiment by critically discussing the different models commonly adopted in the interpretation of spectroscopic experiments and the simulation of particular observables. Thereby, we review all the studies of excited state dynamics on transition metal complexes, both in gas phase and in solution from reduced to full dimensionality.
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