IndraLab
Statements
sparser
"All electronic structure calculations
were performed with the ORCA
software package (version 5.0.3). xref Each
set of calculations was conducted using five different density functionals:
the hybrid density functionals PBE0 xref , xref and B3LYP, xref , xref as well as the range-separated hybrid functionals LRC-ωPBEh, xref CAM-B3LYP, xref and
ωB97X. xref No optimization of the range-separation
parameter ω was done."
sparser
"Of the tested density functionals,
ωB97X predicts geometries closest to the experimental ones using
the isolated models, resulting in an average RMSD value of 0.58 Å,
whereas the B3LYP functional shows the largest deviation with an average
RMSD of 0.67 Å. With the QM/MM models, however, the difference
between the tested functionals is mostly negligible, with PBE0, LRC-ωPBEh,
and ωB97X reaching an average RMSD of 0.18 Å, followed
by CAM-B3LYP and B3LYP with RMSD values of 0.19 Å and 0.21 Å,
respectively."
sparser
"They demonstrated that the overestimation by 0.5 eV (in respect to the experimental data) of the transition energy for the relevant TPA state in [5,15-bis(3,5-bitert-butylphenyl)-10,20-bis(trihexylsilylethynyl)porphyrinato]zinc by B3LYP led to a 5-fold overprediction of the TPA cross-section for this molecule, whereas for 5,5′-(ethyne)bis[[10,20-bis(3,5-bitert- butylphenyl)-porphyrinato]zinc], underestimation of the transition energy by 0.5 eV with CAM-B3LYP and by 0.8 eV with B3LYP lead to underestimations of the TPA cross-section by factors of 2 and 4, respectively [ xref ]."
| PMC
sparser
"The anodic limit of the 27 anions was calculated by means of Equations (1) and (2) using different DFT functionals with different levels of complexity in a vacuum: B3LYP (Global Hybrid Generalized Gradient Approximation, GH-GGA), ωB87X-D and CAM-B3LYP (Range-Separated Hybrid Generalized Gradient Approximation, RSH-GGA), M11-L and BMK (meta-Generalized Gradient Approximation, mGGA), M06-2X and M08-HX (Global Hybrid meta-Generalized Gradient Approximation, GH-mGGA), MN-12SX, M11, ωB87M-V (Range-Separated Hybrid meta-Generalized Gradient Approximation, RSH-mGGA)."
sparser
"Interestingly, for
the CAM-B3LYP functional, the deviations with respect to experiment
are almost identical (albeit with a reversed sign) between the two
models, with the isolated model slightly underestimating the fluorescence
energies, whereas the QM/MM model tends to overestimate them, as indicated
by the MSDs of −0.18 and 0.19 eV."
sparser
"Comparing the isolated
models in solution against experimental
excitation energies, the same relative trend is observed (in increasing
MAD): PBE0 < B3LYP < LRC-ωPBEh < CAM-B3LYP ≪
ωB97X. As in the solid state, the hybrid functionals predict
slightly underestimated excitation energies, while the range-separated
hybrids overestimate the transition energies ( xref )."
sparser
"After careful investigation of the thermochemical
and kinetic studies of the PAHs, we have decided to test 6 different
functionals from the fourth rung of the Jacob’s Ladder (B3LYP, xref CAM-B3LYP, xref LC-WPBE, xref M05-2X-D3 xref , xref M06-2X-D3 32 and WB97XD xref and three different functionals from the fifth
rung of the Jacob’s Ladder (B2PLYP, xref DSDPBEP86, xref PBE0DH xref )."
sparser
"It is worth noting how the B3LYP shows the largest errors (∼ −0.2 eV), while TD‐CAM‐B3LYP/6‐31++G(d,p)/C‐PCM provides the best match also with the experiment (in addition to be, CAM‐B3LYP, the best match in the same conditions with the reference level as shown before), with a blue shift of less than 0.1 eV."
sparser
"This is motivated by the presence of the CAM‐B3LYP functional, as reported previously is the recommended functional for describing CT electronic excitations by the presence of a more complete basis set, with the introduction of the diffuse functions, that increases the accuracy of the results and by the presence of the solvent to reproduce the experimental conditions."
sparser
"To gauge the accuracy of the TD‐DFT/C‐PCM combined potential and to perform the best choice for our study, we tested the performance of the B3LYP and the CAM‐B3LYP density functionals with both the LR and SS C‐PCM formalisms starting from the optimized geometry of the stable isomer computed at B3LYP/6‐31G(d,p)/C‐PCM cyclohexane level of theory."
sparser
"Our main result is the identification of two cost‐effective theory levels: one for the ground state, using the B3LYP functional with the 6‐31G(d,p) basis set and the conductor‐like polarizable continuum model for solvation, and another for the excited states, employing the Coulomb‐Attenuating Method version (CAM‐B3LYP) functional with the double‐ζsplit‐valence basis set with polarization and diffuse functions and the linear response C‐PCM solvation model."
sparser
"For the CAM-B3LYP functional, it can be
seen that the overall accuracy of the two dispersion corrections is
nearly identical, but the GD3 correction performs slightly better
on ionic/electrostatic interactions, and GD3BJ performs better on
hydrogen-bond/electrostatic interactions."
sparser
"The lowest value, indicating the highest data dispersion, are observed for CAM–B3LYP with and without dispersion correction (0.90–0.91), followed byωB97X(D4, without), TPSS0(D3BJ, D3zero, D4, without), B3LYP(D3BJ, D3zero, D4, without),ωB97(D4, without), and M06(D3zero, without), which lie in the range of 0.92 to 0.93."
sparser
"As shown in Figure xref , as the basis set size increases, the B3LYP, B3P86, PBE0, MP2, ωB97XD, and CAM‐B3LYP methods appear to converge to energy differences that agree much better with the experimental value and, in all cases, predict the trans conformer to be more stable than the cis ."
sparser
"It is of interest whether the values of H strain are reproducible using other functionals since any functional chosen leads to different absolute electronic energy values. xref Therefore, for all structures optimised with B3LYP*, the calculations of the electronic energies were performed also with CAM-B3LYP xref and B3LYP xref using the CEP-31G basis set ( xref )."
sparser
"However, it is worth noting thatωB97(D4, without),ωB97X(D4, without), and CAM–B3LYP(D3BJ, D3zero, D4, without), despite exhibiting relatively lowR2values, also show the largest slopes of the linear regression (0.84–0.80), indicating that these functionals follow the experimental trends more closely."
sparser
"For Fe–Fe/Mo–Fe distances,
CAM-B3LYP gives worse deviations for both spin-coupled (and diamagnetic
complexes) than its parent B3LYP functional with MD = +0.061 Å
(MAD 0.067 Å) and the recent ωB97M-D3BJ functional (found
to be highly accurate for main group thermochemistry) xref , xref offers no improvement either, with MD of +0.067 Å (MAD = 0.067
Å)."
sparser
"The effects of multiple substitutions on the electride characteristics and the second-order NLO properties ( β 0 ) of Li@calix[4]pyrrole (1) and its analogues (octafluorine-1, octamethoxy-1 and tetra-lithium-1) were theoretically studied at the CAM-B3LYP and MP2 levels of theory."
sparser
"The lowest MAE value are obtained with TPSS0, both with dispersion corrections (D3BJ, D3zero, D4) and without (0.015–0.016), followed by TPSSh(D3BJ, D3zero, D4, without), PBE0(D3BJ, D3zero, D4, without), CAM–B3LYP(D3BJ, D4), B3LYP(D4), and r 2 SCAN(D3BJ, D4, without), all within the range of 0.016–0.018."
sparser
"When considering the overall structural deviations through RMSD analysis, the same trend is observed: TPSS0, TPSSh, CAM–B3LYP, r 2 SCAN, and M06 yield the best agreement with experimental, whereas RPBE, revPBE,ωB97, and M06L perform the worst, with substantially larger RMSD values."
sparser
"On the other hand, CAM–B3LYP(D3BJ, D3zero, D4, without), M06(D3zero, without), PBE0(D3BJ, D3zero, D4, without), TPSS0(D3BJ, D3zero, D4, without),ωB97(D4, without), and ωB97X(D4, without) show the highest deviations (from 37 to 42 cm −1 ), indicating that the calculated frequencies are more distant from the experimental ones."
sparser
"Atomic charges based on Hirshfeld charges, Fukui functions (), Mulliken and Natural population analysis (NPA) for BFDP molecule sites using CAM−B3LYP at 6−311G++(d,p) level were presented in xref Considering the terms mentioned previously, the relatively higher degree of reactivity descriptors () found around the O1 atom indicates the highest potential for nucleophilic attack at this particular location."
sparser
"According to the Hirshfeld, Mulliken and natural population analysis charges, F1, F2, N1 and O1 atoms display significant negative atomic loads in the crystalline compound having the following amounts of CAM-B3LYP functional values: 0.1019, −0.1019, −0.0712 and −0.2607/−0.1789, −0.1784, 0.2055 and −0.2330/−0.3575, −0.3574, −0.6929 and −0.5593, respectively."
sparser
"Time-dependent DFT (TD-DFT) analyses were performed
on the π-stacked
D–A dimers and D–A–D–A tetramers using
the coordinates obtained from low-temperature experimental geometry
with the optically tuned and range-separated functional CAM-B3LYP
to understand the effect of charge transfer on optical properties."
sparser
"This observation is also validated
by examining R 2 values (0.9931 for TD-B3LYP,
0.9906 for TD-M06-2X, 0.9909 for PBEPBE, 0.9915 for BMK, 0.9936 for
wB97XD, 0.9935 for CAM-B3LYP, and 0.9928 for CIS) calculated for correlation
of the calculated excited-state frequencies with those of the experiment."
sparser
"In summary, our study shows that for the two modelled systems (1 and 2) E ad values obtained with B3LYP and CAM-B3LYP functionals (and geometries from B3LYP*) all HS state turns to be the ground state above 200 K. The B3LYP/D3 approach predicts all HS state to be the ground state of 1 above 100 K and over 200 K for 2."
sparser
"Although the CAM-B3LYP and B3LYP spectra of Acebutolol are similar (Fig. S6 xref ), the CAM-B3LYP spectrum has the primary bands at shorter wavelengths (219 (H−3 → L/H → L+1) and 304 nm (H → L)). xref , shows the computed B3LYP electronic spectrum of Acebutolol, the descriptions and energies of selected frontiers molecular orbitals."
sparser
"For 1 and 2 the further optimization were performed with CAM-B3LYP xref functionals and the CEP-31G basis. xref Additionally, the PBEh functional was used for the above two systems. xref In order to check the dependence of the obtained H coop parameters the relevant four isomers of 1, 2 and 2a were optimised with B3LYP, CAM-B3LYP and TPSS xref functionals with Grimme's D3 dispersion correction. xref The CEP-31G basis set was used for the former and the tzvp xref for the latter one."
sparser
"What is even more puzzling, though, is that the CBDE radical anion (which, as a 3-electron 4-center system must host the Jahn–Teller effect in D 4h geometry) is computed by some DFT methods (e.g., CAM-B3LYP with either 6-31G(d,p) or cc-pVDZ basis set) to be an undistorted square."
sparser
"Definitionally, softness is the hardness ( η = ( I − A )/2) reciprocal. xref The energy reduction brought about by the maximum electron flow between the donor and acceptor is measured by the electrophilicity index, ω = (− χ 2 /2 η ). xref Natural bonding orbitals (NBO) analysis of Weinhold and co-workers were carried out at the same level of theory of the optimization process xref Time-dependent density functional theory (TDDFT) computations were carried out utilizing two distinct level of theories; B3LYP xref /6-31G(d) and a Coulomb-attenuated hybrid exchange-correlation functional, CAM-B3LYP xref /6-31G(d), with PCM solvation model."
sparser
"Further energy calculations with the B3LYP and CAM-B3LYP functionals for the geometry of the spin isomers optimised with B3LYP* exhibit that each spin transition energy from the fully LS state to a given spin isomer may be considered as the sum of the functional-dependent quantity E ad (derived from the calculated spin transition energy from the fully LS to the fully HS state) and the functional independent H strain ."
sparser
"The β HRS values (×10 −30 esu) of helicenes H1–H14 are calculated by using CAM-B3LYP functionals associated with the 6-31+G(d) basis set and the β HRS values (×10 −30 esu) of helicenes H15–H28 are calculated by using CAM-B3LYP associated with the 6-31+G(d) for O, N, C and H atoms and LANL2DZ basis set for Se atom."
sparser
"Previous studies also have shown that the B3LYP functional overestimates β HRS. xref and the CAM-B3LYP functional combined with 6-31+G(d) basis set is a reliable method to calculate β HRS . xref Thus, the β HRS values obtained by CAM-B3LYP/6-31+G(d) level functional were used for further analysis."
sparser
"Ground-state geometry optimization and harmonic frequency analysis of the complexes were executed using B3LYP (ref. xref ) functional and the effective core potential (ECP) of the Hady and Wadt, LANL2DZ basis set. xref In the singlet state, TDDFT calculations were performed at CAM-B3LYP (ref. xref )/LANL2DZ level of theory and the PCM keyword to introduce the effect of the solvent."
sparser
"The time-dependent density functional theory (TD-DFT) calculations were investigated with the CAM-B3LYP functional [ xref ] since it gives rise to more reliable results compared to pure B3LYP on the nature of electronic transitions spectra to get further insights into the electronic absorption of T-705–nanocage complexes in the gas and aqueous phases."
sparser
"The AEA value is the energy difference between the
global minimal configurations of neutral and anion, and the VDE value
is the energy difference between the anionic global minimal configuration
of neutral and anionThe VDE and AEA computed at PBE0, B3LYP, and
CAM-B3LYP functionals, and experimentally measured values are presented
in xref ."
sparser
"At the same
time, UV–vis spectra were calculated using TDDFT with PBE,
PBE0, B3LYP, and CAM-B3LYP functionals, in order to analyze the transitions
in 120 excited states, which are enough to describe the characteristics.shows that the strongest absorption
bands are situated in the near-ultraviolet regions."
sparser
"In 2010, Pastore et al. benchmarked DFT and TD-DFT methods
with
the 6-31G(d) basis set to predict S 0 and S 1 oxidation
potentials for four triphenylamine dyes. xref MPW1K xref and CAM-B3LYP xref provided balanced descriptions of S 0 and S 1 oxidation potentials, with errors ranging from 0.2 to 0.3
eV. xref In 2018, McCarthy et al. predicted
the T 1 reduction potentials of 14 phenoxazines using M06 xref /6-311+G(d,p). xref In
2018, Singh and co-workers computed the redox potentials of OPCs in
the T 1 excited state using the B3LYP xref /6-311G(d) model chemistry. xref In 2021, Choi and Kim computed the redox potentials for quinoxalines
by performing geometry optimization with B3LYP xref /6-311++G(d,p) density functional and energy refinement
by spin-flip DFT; the mean signed deviations were −0.15 eV
for ground state and 0.01 eV for S 1 excited state. xref Feher and co-workers recently benchmarked computational
approaches to predict S 0 and S 1 redox potentials
for 37 OPCs."
sparser
"Unsurprisingly, ωB97X is
also the only functional with negligible difference in the predicted
excitation energy between the two models, while the PBE0, LRC-ωPBEh,
B3LYP, and CAM-B3LYP functionals show an absolute difference in the
excitation energy of 0.19, 0.25, 0.14, and 0.28 eV, respectively ()."
sparser
"In the singlet
excited states Kim, Nakano, Yamago, and co-workers recently revealed
rapid interconversion between self-trapped exciton and delocalized
states, xref yet it has earlier been found
through time-dependent CAM-B3LYP calculations that the S 1 state of [ n ]CPP ’s
is more delocalized than the T 1 state. xref Similar observations in the T 1 state of various [ n ]CPP ’s could give experimental
support as to which functional gives the right description: UB3LYP
or UCAM-B3LYP?"
sparser
"The rate-determining
step can be either the bond rotation or the proton transfer, depending
on the rotating bond and the meso -substituents. xref , xref For this particular switch, several density functionals were benchmarked
against CCSD(T)/6-31G data, concluding that both CAM-B3LYP and M05-2X
provide the most reliable results. xref Besides
the Hückel–Möbius interconversion, we also considered
the switching from 28M to 28F with the associated
transition state ( 28TS 3 ), as
shown in."
sparser
"Range-separated
hybrid functionals show significantly poorer performance
compared to the meta -GGA hybrids, except for CAM-B3LYP-D3
(RMSD = 1.8 kcal mol –1 ), as pointed out in previous
benchmark studies on expanded porphyrins. xref , xref We recently proved that M06-2X and CAM-B3LYP exhibit very similar
degrees of π-electron delocalization in expanded porphyrins. xref Disappointingly, the promising range-separated
hybrid ωB97M-V with nonlocal correlation, xref designed using a combinatorial approach and containing
only 12 parameters, clearly underperforms the older ωB97XD for
topology interconversions in expanded porphyrins."