Appendix A
Table A1.
Parameters used in the Ewald program.
Table A1.
Parameters used in the Ewald program.
Crystal | Zone 1 | Number of Charges | Unit Cell Composition | Supercell | Total |
---|
| Composition | in Zone 2 | | “Zones 1 + 2 + 3” | Number |
---|
| (Number of Atoms ) | (Diameter of Zone 2) | | Dimensions | of Atoms a |
---|
PYV3 | PYV3 (29) | 4971 (44 Å) | 4 PYV3 | 16 × 10 × 4 | 74,240 |
PYV3 SA | PYV3 + SA (43) | 9957 (56 Å) | 4 PYV3 + 2 SA | 20 × 4 × 10 | 115,200 |
PYV3 FA1 | PYV3 + FA (41) | 9959 (56 Å) | 4 PYV3 + 2 FA | 20 × 4 × 10 | 112,000 |
Table A2.
Ahlrichs basis sets and their contracted compositions for the atoms in PYV3 I2but.
Table A2.
Ahlrichs basis sets and their contracted compositions for the atoms in PYV3 I2but.
Basis Set | Composition | |
---|
def2-SVP | C, N, O, F | 3s 2p 1d |
| I | 4s 4p 2d |
| H | 2s 1p |
def2-SVPD | C, N | 4s 2p 2d |
| O, F | 4s 3p 2d |
| I | 5s 5p 3d |
| H | 2s 2p |
def2-TZVP | C, N, O, F | 5s 3p 2d 1f |
| I | 6s 5p 3d 2f |
| H | 3s 1p |
def2-TZVPP | C, N, O, F, I | def2-TZVP |
| H | 3s 2p 1d |
def2-TZVPD | C, N | 6s 3p 3d 1f |
| O, F | 6s 4p 3d 1f |
| I | 7s 6p 4d 2f |
| H | 3s 2p |
def2-TZVPPD | C, N, O, F, I | def2-TZVPD |
| H | 3s 3p 1d |
def2-QZVP | C, N, O, F | 7s 4p 3d 2f 1g |
| I | 7s 6p 4d 4f 1g |
| H | 4s 3p 2d 1f |
Table A3.
Contributions of the and clusters to the RI-CC2 and RI-CCSD excited states of the enol and keto forms of the isolated PYV3 [PYV3] molecule (in %), as calculated with the def2-TZVPD basis set.
Table A3.
Contributions of the and clusters to the RI-CC2 and RI-CCSD excited states of the enol and keto forms of the isolated PYV3 [PYV3] molecule (in %), as calculated with the def2-TZVPD basis set.
| Enol |
---|
| RI-CC2 | RI-CCSD |
---|
State | | | | |
---|
1 | 87.14 | 12.86 | 92.17 | 7.83 |
2 | 88.96 | 11.04 | 92.98 | 7.02 |
3 | 87.64 | 12.36 | 92.93 | 7.07 |
4 | 87.62 | 12.38 | 91.56 | 8.44 |
5 | 88.84 | 11.16 | 92.94 | 7.06 |
| Keto |
1 | 87.38 | 12.62 | 91.79 | 8.21 |
2 | 85.49 | 14.51 | 92.31 | 7.69 |
3 | 87.62 | 12.38 | 92.42 | 7.58 |
4 | 86.55 | 13.45 | 91.78 | 8.22 |
5 | 89.25 | 10.75 | 94.45 | 5.55 |
Table A4.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the enol PYV3 molecule in its crystal (PYV3 [PYV3]) and its co-crystals (PYV3 [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
Table A4.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the enol PYV3 molecule in its crystal (PYV3 [PYV3]) and its co-crystals (PYV3 [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
| 2nd Absorption Band |
---|
| 2nd Excitation | | 3rd Excitation |
---|
Crystal | | f | | | f |
---|
PYV3 [PYV3] | 293 | 0.466 | | 273 | 0.144 |
PYV3 [PYV3 SA] | −3 | +10% | | +3 | −75% |
PYV3 [PYV3 FA1] | −2 | +11% | | +4 | −73% |
PYV3 [PYV3 FA2] | +2 | −24% | | +2 | +13% |
PYV3 [PYV3 DHBP] | −1 | +8% | | +4 | −45% |
PYV3 [PYV3 SDP] | −2 | +54% | | — |
PYV3 [PYV3 I2but] | +8 | −75% | | +9 | +301% |
PYV3 [PYV3 I2F4] | +11 | −72% | | +10 | +287% |
PYV3-N [PYV3 I3F3] | −4 | −89% | | 0 | +356% |
PYV3-O [PYV3 I3F3] | −11 | −75% | | −8 | +267% |
Table A5.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the keto PYV3 molecule in its crystal (PYV3 [PYV3]) and its co-crystals (PYV3 [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
Table A5.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the keto PYV3 molecule in its crystal (PYV3 [PYV3]) and its co-crystals (PYV3 [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
| 2nd Absorption Band |
---|
| 3rd Excitation |
---|
| | |
PYV3 [PYV3] | 304 | 0.476 |
PYV3 [PYV3 SA] | −3 | −3% |
PYV3 [PYV3 FA1] | −2 | −2% |
PYV3 [PYV3 FA2] | 0 | 0% |
PYV3 [PYV3 DHBP] | 0 | 0% |
PYV3 [PYV3 SDP] | +6 | +4% |
PYV3 [PYV3 I2but] | +4 | +1% |
PYV3 [PYV3 I2F4] | +3 | +1% |
PYV3-N [PYV3 I3F3] | 0 | +1% |
PYV3-O [PYV3 I3F3] | −11 | −3% |
Table A6.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the enol forms of isolated PYV3 (PYV3 [PYV3]) and the heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
Table A6.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the enol forms of isolated PYV3 (PYV3 [PYV3]) and the heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
| 2nd Absorption Band |
---|
| 2nd Excitation | | 3rd Excitation |
---|
Crystal | | f | | | f |
---|
PYV3 [PYV3] | 293 | 0.466 | | 273 | 0.144 |
PYV3 + SA [PYV3 SA] | −3 | +30% | | −6 | −8% |
PYV3 + FA [PYV3 FA1] a | −2 | +33% | | −6 | −12% |
Table A7.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the keto forms of isolated PYV3 (PYV3 [PYV3]) and the heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
Table A7.
RI-CC2/def2-TZVPD wavelengths of excitation, in , and oscillator strengths, f, for the keto forms of isolated PYV3 (PYV3 [PYV3]) and the heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals, the absolute variations and relative variations are given for the wavelengths and oscillator strengths, respectively.
| 2nd Absorption Band |
---|
| 3rd Excitation |
---|
Crystal | | f |
---|
PYV3 [PYV3] | 304 | 0.476 |
PYV3 + SA [PYV3 SA] | 0 | 0% |
PYV3 + FA [PYV3 FA1] | 0 | 0% |
Table A8.
RI-CC2/def2-TZVPD wavelengths of excitation ( in ) and oscillator strengths (f) for the enol forms of the isolated and embedded PYV3 (PYV3 [PYV3]) and the embedded heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals the absolute variations and relative variations with respect to the embedded PYV3 are given for the wavelengths and oscillator strengths, respectively.
Table A8.
RI-CC2/def2-TZVPD wavelengths of excitation ( in ) and oscillator strengths (f) for the enol forms of the isolated and embedded PYV3 (PYV3 [PYV3]) and the embedded heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals the absolute variations and relative variations with respect to the embedded PYV3 are given for the wavelengths and oscillator strengths, respectively.
| | 2nd Absorption Band |
---|
| | 2nd Excitation | | 3rd Excitation |
---|
Crystal | | | f | | | f |
---|
PYV3 [PYV3] | (iso) | 293 | 0.466 | | 273 | 0.144 |
PYV3 [PYV3] | (emb) | 287 | 0.495 | | 264 | 0.214 |
PYV3 + SA [PYV3 SA] | (emb) | −1 | +26% | | 0 | −22% |
PYV3 + FA [PYV3 FA1] a | (emb) | 0 | +27% | | 0 | −22% |
Table A9.
RI-CC2/def2-TZVPD wavelengths of excitation (, in ) and oscillator strengths (f) for the keto forms of the isolated and embedded PYV3 (PYV3 [PYV3]) and the embedded heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals the absolute variations and relative variations with respect to the embedded PYV3 are given for the wavelengths and oscillator strengths, respectively.
Table A9.
RI-CC2/def2-TZVPD wavelengths of excitation (, in ) and oscillator strengths (f) for the keto forms of the isolated and embedded PYV3 (PYV3 [PYV3]) and the embedded heteromers of its co-crystals (PYV3 + XXX [PYV3 XXX]). For PYV3 [PYV3], the absolute values are given while for the co-crystals the absolute variations and relative variations with respect to the embedded PYV3 are given for the wavelengths and oscillator strengths, respectively.
| | 2nd Absorption Band |
---|
| | 3rd Excitation | | 4th Excitation |
---|
Crystal | | | f | | | f |
---|
PYV3 [PYV3] | (iso) | 304 | 0.476 | | — |
PYV3 [PYV3] | (emb) | 299 | 0.536 | | — |
PYV3 + SA [PYV3 SA] | (emb) | +1 | −33% | | −6 | −61% |
PYV3 + FA [PYV3 FA1] | (emb) | +2 | −38% | | −5 | −54% |
Figure A1.
def2-TZVPD NTOs (holes below the arrows and particles above them, the red (green) lobes
are the positive (negative) ones) of the isolated PYV3 [PYV3] enol form (isovalue of 0.02 a.u.).
Figure A1.
def2-TZVPD NTOs (holes below the arrows and particles above them, the red (green) lobes
are the positive (negative) ones) of the isolated PYV3 [PYV3] enol form (isovalue of 0.02 a.u.).
Figure A2.
def2-TZVPD NTOs (holes below the arrows and particles above them, the red (green) lobes
are the positive (negative) ones) of the isolated PYV3 [PYV3] keto form (isovalue of 0.02 a.u.).
Figure A2.
def2-TZVPD NTOs (holes below the arrows and particles above them, the red (green) lobes
are the positive (negative) ones) of the isolated PYV3 [PYV3] keto form (isovalue of 0.02 a.u.).
Figure A3.
RI-CC2/def2-TZVPD UV/Vis absorption spectra of all models considered for PYV3 and
PYV3 FA1.
Figure A3.
RI-CC2/def2-TZVPD UV/Vis absorption spectra of all models considered for PYV3 and
PYV3 FA1.
Figure A4.
RI-CC2/def2-TZVPD NTOs (holes below the arrows and particles above them, the red
(green) lobes are the positive (negative) ones) of the 3rd excited state of the isolated PYV3 [PYV3] enol
form and of the 4th excited state of the isolated and embedded PYV3 + FA [PYV3 FA1] (isovalue
of 0.02 a.u.).
Figure A4.
RI-CC2/def2-TZVPD NTOs (holes below the arrows and particles above them, the red
(green) lobes are the positive (negative) ones) of the 3rd excited state of the isolated PYV3 [PYV3] enol
form and of the 4th excited state of the isolated and embedded PYV3 + FA [PYV3 FA1] (isovalue
of 0.02 a.u.).
Figure A5.
RI-CC2/def2-TZVPD NTOs (holes below the arrows and particles above them, the red
(green) lobes are the positive (negative) ones) of the isolated and embedded PYV3 [PYV3] enol form
(isovalue of 0.02 a.u.).
Figure A5.
RI-CC2/def2-TZVPD NTOs (holes below the arrows and particles above them, the red
(green) lobes are the positive (negative) ones) of the isolated and embedded PYV3 [PYV3] enol form
(isovalue of 0.02 a.u.).
Figure A6.
RI-CC2/def2-TZVPD NTOs (holes below the arrows and particles above them, the red
(green) lobes are the positive (negative) ones) of the isolated and embedded PYV3 [PYV3] keto form
(isovalue of 0.02 a.u.).
Figure A6.
RI-CC2/def2-TZVPD NTOs (holes below the arrows and particles above them, the red
(green) lobes are the positive (negative) ones) of the isolated and embedded PYV3 [PYV3] keto form
(isovalue of 0.02 a.u.).
Figure A7.
RI-CC2 def2-SVPD (SV) and def2-TZVPD (TZ) NTOs (holes below the arrows and particles above them, the red (green) lobes are the positive (negative)
ones) of the embedded PYV3 + SA [PYV3 SA] enol form (isovalue of 0.02 a.u.).
Figure A7.
RI-CC2 def2-SVPD (SV) and def2-TZVPD (TZ) NTOs (holes below the arrows and particles above them, the red (green) lobes are the positive (negative)
ones) of the embedded PYV3 + SA [PYV3 SA] enol form (isovalue of 0.02 a.u.).
Figure A8.
RI-CC2 def2-SVPD (SV) and def2-TZVPD (TZ) NTOs (holes below the arrows and particles above them, the red (green) lobes are the positive (negative)
ones) of the embedded PYV3 + SA [PYV3 SA] keto form (isovalue of 0.02 a.u.).
Figure A8.
RI-CC2 def2-SVPD (SV) and def2-TZVPD (TZ) NTOs (holes below the arrows and particles above them, the red (green) lobes are the positive (negative)
ones) of the embedded PYV3 + SA [PYV3 SA] keto form (isovalue of 0.02 a.u.).