Complementary Information Martínez-Barbosa
H-Dissociation energies for the different sites.
BDE (eV)/ 7-Xap / 4.23
/ 7-Xap-HC / 4.86
/ 7-Xap-HN1 / 4.78
/ 7-Xap-HN3 / 4.65
/ Lcp / 3.72
/ Lcp-H1 / 4.41
/ Lcp-H2 / 4.60
/ Lcp-H3 / 4.45
/ Bip / 3.43
/ Bip-HCH3 / 4.59
/ Bip-HN1 / 4.83
/ Bip-HN2 / 4.35
/ Bip-HO2 / 3.49
/ Bip-HOH1 / 4.66
/ Bip-HOH2 / 4.13
/ Ptr / 4.18
/ Ptr-H1 / 4.89
/ Ptr-HC1 / 4.80
/ Ptr-HC2 / 4.69
/ Xap / 3.82
/ Xap-H2 / 4.23
/ Xap-HC / 4.80
/ Xap-HN / 4.48
/ Sep / 3.19
/ Sep-H1 / 3.43
/ Sep-HN1 / 4.20
/ Sep-HN3 / 4.25
/ Sep-HOH / 4.00
/ H2Bip / 3.06
/ H2Bip-H1 / 3.11
/ H2Bip-H2 / 4.18
/ H2Bip-H3 / 4.02
/ H2Bip-H4 / 4.15
/ H2Bip-H5 / 4.57
/ H2Bip-HOH / 3.47
/ BH4 / 3.40
/ BH4-NH2 / 3.52
/ BH4-NH1 / 3.70
/ BH4-H2 / 3.93
/ BH4-H1 / 4.01
/ BH4-OH1 / 4.09
/ BH4-OH2 / 4.22
OPTIMIZED STRUCTURES
Isoxanthoptherin
# Opt Freq bpw91/6-311+G(d) pop=nbo
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.003075 -0.041394 -0.002505
2 6 0 0.001157 -0.027725 2.267580
3 6 0 1.405367 0.018753 2.387864
4 6 0 2.201245 0.027810 1.165487
5 8 0 3.414067 0.052189 1.028817
6 6 0 -0.160557 -0.017789 4.727315
7 6 0 1.309427 0.029764 4.691641
8 7 0 2.032970 0.045871 3.604350
9 7 0 -0.722706 -0.044909 3.430016
10 7 0 -0.712048 -0.046605 1.109257
11 7 0 1.369047 -0.004108 -0.011070
12 7 0 -0.649609 -0.121914 -1.203325
13 1 0 -1.655595 0.002597 -1.155397
14 1 0 -0.202984 0.213886 -2.049323
15 1 0 1.893318 -0.051551 -0.883718
16 1 0 1.820006 0.052864 5.658806
17 8 0 -0.868802 -0.033861 5.730353
18 1 0 -1.740645 -0.078442 3.362191
------
Isoxanthoptherin IN WATER (neutral)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -0.065124 0.062877 0.119400
2 6 0 -0.031727 0.005145 2.393008
3 6 0 1.381623 0.031769 2.475222
4 6 0 2.133750 0.079321 1.229691
5 8 0 3.364240 0.107470 1.099701
6 6 0 -0.115515 -0.056852 4.839016
7 6 0 1.346159 -0.026633 4.781294
8 7 0 2.041522 0.014935 3.669038
9 7 0 -0.720263 -0.038638 3.579463
10 7 0 -0.761302 0.018613 1.259396
11 7 0 1.307788 0.093357 0.088240
12 7 0 -0.723243 0.078842 -1.050915
13 1 0 -1.745567 0.055534 -1.046454
14 1 0 -0.238227 0.109372 -1.951297
15 1 0 1.799197 0.130490 -0.825003
16 1 0 1.884369 -0.039710 5.737109
17 8 0 -0.791963 -0.095225 5.880850
18 1 0 -1.758276 -0.058861 3.541514
------
Isoxanthoptherin IN WATER (cation)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -2.083031 -0.873891 -0.009320
2 6 0 0.196129 -0.672393 0.019269
3 6 0 0.130381 0.775921 0.029264
4 6 0 -1.214630 1.405985 0.020940
5 8 0 -1.414751 2.613253 0.030162
6 6 0 2.614136 -0.480741 0.048677
7 6 0 2.399728 0.984531 0.054435
8 7 0 1.215801 1.569720 0.046055
9 7 0 1.438038 -1.231444 0.030453
10 7 0 -0.863207 -1.466466 0.001083
11 7 0 -2.262582 0.482541 0.000930
12 7 0 -3.144474 -1.667371 -0.029821
13 1 0 -3.006304 -2.686643 -0.037456
14 1 0 -4.107099 -1.302361 -0.040947
15 1 0 -3.228133 0.879587 -0.006535
16 1 0 3.297632 1.616931 0.066847
17 8 0 3.728116 -1.001213 0.057970
18 1 0 1.518898 -2.273349 0.024989
------
Isoxanthoptherin IN WATER (anion)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.003340 -0.057025 -0.004358
2 6 0 -0.004134 -0.027293 2.283916
3 6 0 1.407152 0.011082 2.408182
4 6 0 2.162219 0.035076 1.173753
5 8 0 3.411274 0.087933 1.048468
6 6 0 -0.151116 -0.016953 4.746415
7 6 0 1.259925 0.014775 4.740001
8 7 0 2.058444 0.035017 3.620103
9 7 0 -0.745012 -0.024987 3.445836
10 7 0 -0.707334 -0.060784 1.118274
11 7 0 1.368136 -0.007570 0.004173
12 7 0 -0.633200 -0.177040 -1.216673
13 1 0 -1.631155 0.049622 -1.198154
14 1 0 -0.145789 0.176443 -2.045543
15 1 0 1.888701 -0.005963 -0.889981
16 1 0 1.769867 0.023411 5.710028
17 8 0 -0.933578 -0.037240 5.752742
18 1 0 -1.772571 -0.061936 3.380989
------
Isoxanthoptherin IN BENZENE (neutral)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.006471 -0.020790 0.007525
2 6 0 -0.015947 -0.020760 2.279760
3 6 0 1.390566 0.014626 2.407122
4 6 0 2.187184 0.032595 1.187387
5 8 0 3.408628 0.060337 1.070991
6 6 0 -0.184355 -0.024730 4.732179
7 6 0 1.282986 0.011668 4.710833
8 7 0 2.012270 0.029720 3.624567
9 7 0 -0.743600 -0.038653 3.441234
10 7 0 -0.718108 -0.034512 1.120949
11 7 0 1.375553 0.012957 0.012227
12 7 0 -0.630961 -0.063032 -1.187119
13 1 0 -1.646215 -0.007994 -1.185109
14 1 0 -0.147278 0.081377 -2.068521
15 1 0 1.902940 0.007937 -0.866583
16 1 0 1.789376 0.023970 5.681801
17 8 0 -0.896468 -0.042568 5.739819
18 1 0 -1.767873 -0.065578 3.369111
------
Isoxanthoptherin IN BENZENE (cation)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf= (solvent=benzene)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -2.090209 -0.873245 -0.009489
2 6 0 0.190797 -0.670639 0.018267
3 6 0 0.136033 0.781151 0.029432
4 6 0 -1.206300 1.418370 0.019000
5 8 0 -1.418701 2.615025 0.025927
6 6 0 2.622325 -0.480142 0.048232
7 6 0 2.406619 0.986334 0.056755
8 7 0 1.222717 1.571181 0.048149
9 7 0 1.429551 -1.231104 0.028047
10 7 0 -0.873285 -1.462690 -0.000323
11 7 0 -2.266139 0.481815 -0.000660
12 7 0 -3.151725 -1.676866 -0.027978
13 1 0 -2.999196 -2.687050 -0.034517
14 1 0 -4.114113 -1.336808 -0.036320
15 1 0 -3.209975 0.892226 -0.008615
16 1 0 3.302307 1.617150 0.071947
17 8 0 3.721940 -1.012672 0.057769
18 1 0 1.512002 -2.259438 0.021373
------
Isoxanthoptherin IN BENZENE (anion)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf= (solvent=benzene)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.021909 -0.070833 -0.015088
2 6 0 0.000373 -0.037969 2.268904
3 6 0 1.413990 0.016109 2.412081
4 6 0 2.192363 0.009683 1.176262
5 8 0 3.430750 0.039568 1.047454
6 6 0 -0.166054 -0.008719 4.742574
7 6 0 1.252932 0.047591 4.733274
8 7 0 2.043930 0.060427 3.614856
9 7 0 -0.746401 -0.052912 3.434683
10 7 0 -0.694604 -0.056867 1.095853
11 7 0 1.392130 -0.055135 0.005927
12 7 0 -0.598737 -0.177408 -1.272486
13 1 0 -1.612805 -0.125283 -1.158669
14 1 0 -0.293293 0.531273 -1.946854
15 1 0 1.919739 -0.141457 -0.866258
16 1 0 1.760406 0.083123 5.701784
17 8 0 -0.946675 -0.021637 5.733516
18 1 0 -1.764783 -0.082985 3.370360
------
Leucopterin
# Opt Freq bpw91/6-311+G(d) pop=nbo
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.008661 -0.051584 -0.005224
2 6 0 0.002407 -0.041689 2.270133
3 6 0 1.383007 0.022567 2.364106
4 6 0 2.181820 0.042119 1.168399
5 8 0 3.411629 0.082623 1.099949
6 6 0 -0.191439 -0.043219 4.743351
7 6 0 1.347867 0.026572 4.832810
8 8 0 1.931375 0.056407 5.904188
9 7 0 2.000715 0.052197 3.608899
10 7 0 -0.724055 -0.072168 3.447029
11 7 0 -0.702241 -0.062475 1.103370
12 7 0 1.380622 -0.001617 -0.008043
13 7 0 -0.629822 -0.152452 -1.221640
14 1 0 -1.637620 -0.039187 -1.162390
15 1 0 -0.208984 0.298493 -2.028395
16 8 0 -0.905123 -0.071929 5.728911
17 1 0 1.908857 -0.063254 -0.877135
18 1 0 3.021371 0.095725 3.623405
19 1 0 -1.741262 -0.118494 3.374863
------
Leucopterin IN WATER (neutral)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -0.066609 0.062373 0.117913
2 6 0 -0.014444 0.006798 2.394862
3 6 0 1.374608 0.031962 2.450782
4 6 0 2.126661 0.077344 1.227796
5 8 0 3.367147 0.103542 1.129638
6 6 0 -0.131925 -0.059072 4.851682
7 6 0 1.396703 -0.030959 4.898750
8 8 0 2.004531 -0.048645 5.977736
9 7 0 2.021749 0.012911 3.682230
10 7 0 -0.705691 -0.036985 3.595557
11 7 0 -0.751664 0.020900 1.260237
12 7 0 1.308038 0.090359 0.085954
13 7 0 -0.725450 0.078149 -1.057977
14 1 0 -1.746830 0.056784 -1.056096
15 1 0 -0.237760 0.107598 -1.955938
16 8 0 -0.806848 -0.099707 5.881858
17 1 0 1.803556 0.122838 -0.825111
18 1 0 3.058761 0.030884 3.691836
19 1 0 -1.743777 -0.055545 3.551407
------
Leucopterin IN WATER (cation)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -0.036013 0.063197 0.118168
2 6 0 -0.048801 0.004938 2.406160
3 6 0 1.379369 0.031008 2.460948
4 6 0 2.144000 0.077562 1.208790
5 8 0 3.370658 0.101648 1.152157
6 6 0 -0.153778 -0.059950 4.852357
7 6 0 1.382837 -0.029949 4.888818
8 8 0 2.006634 -0.043980 5.935714
9 7 0 2.023151 0.013154 3.646308
10 7 0 -0.735332 -0.038685 3.591326
11 7 0 -0.737406 0.020665 1.273239
12 7 0 1.333873 0.091210 0.075449
13 7 0 -0.715033 0.078200 -1.023057
14 1 0 -1.741869 0.056485 -0.994121
15 1 0 -0.250601 0.108402 -1.940186
16 8 0 -0.808845 -0.099826 5.880102
17 1 0 1.827191 0.123367 -0.843641
18 1 0 3.069883 0.031651 3.665387
19 1 0 -1.779161 -0.057571 3.549197
------
Leucopterin IN WATER (anion)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=water)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.001016 -0.048390 -0.012174
2 6 0 -0.002138 -0.072410 2.279236
3 6 0 1.396497 -0.027843 2.357442
4 6 0 2.158938 0.018428 1.160897
5 8 0 3.416114 0.063195 1.068476
6 6 0 -0.137801 -0.017178 4.765170
7 6 0 1.299749 0.027574 4.841416
8 8 0 1.967482 0.120196 5.924100
9 7 0 2.008141 -0.062384 3.617015
10 7 0 -0.706400 -0.106543 3.449642
11 7 0 -0.708786 -0.079743 1.109373
12 7 0 1.366649 0.008752 -0.016539
13 7 0 -0.638210 -0.131604 -1.220529
14 1 0 -1.640770 0.071122 -1.201994
15 1 0 -0.149539 0.210232 -2.052886
16 8 0 -0.943294 0.017169 5.758769
17 1 0 1.884351 0.025110 -0.912093
18 1 0 3.023122 0.091791 3.669285
19 1 0 -1.736295 -0.124794 3.397851
------
Leucopterin IN BENZENE (neutral)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=benzene)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.003736 -0.042215 -0.002311
2 6 0 0.001242 -0.033795 2.274499
3 6 0 1.384605 0.012466 2.365860
4 6 0 2.174534 0.030476 1.165759
5 8 0 3.409254 0.066148 1.094920
6 6 0 -0.185763 -0.031260 4.739739
7 6 0 1.349399 0.019665 4.826614
8 8 0 1.931521 0.044362 5.906327
9 7 0 2.002911 0.036011 3.611656
10 7 0 -0.722787 -0.054058 3.454253
11 7 0 -0.706039 -0.051567 1.113987
12 7 0 1.376567 -0.001775 -0.004224
13 7 0 -0.634808 -0.126607 -1.207273
14 1 0 -1.643546 0.008707 -1.178937
15 1 0 -0.172725 0.207677 -2.050057
16 8 0 -0.893489 -0.050079 5.736591
17 1 0 1.902410 -0.031636 -0.883669
18 1 0 3.028861 0.069030 3.635134
19 1 0 -1.747058 -0.088871 3.383588
------
Leucopterin IN BENZENE (cation)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=benzene)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -0.032624 0.063052 0.111094
2 6 0 -0.048040 0.005389 2.402954
3 6 0 1.380317 0.031093 2.462252
4 6 0 2.151318 0.078151 1.215227
5 8 0 3.372221 0.103777 1.161342
6 6 0 -0.156636 -0.059638 4.865657
7 6 0 1.386071 -0.031812 4.906471
8 8 0 2.015232 -0.046788 5.939339
9 7 0 2.026236 0.012921 3.647139
10 7 0 -0.735511 -0.037881 3.583634
11 7 0 -0.730626 0.021247 1.262421
12 7 0 1.338227 0.090932 0.069017
13 7 0 -0.722186 0.077402 -1.030298
14 1 0 -1.742052 0.056250 -0.984121
15 1 0 -0.285000 0.107065 -1.951488
16 8 0 -0.822475 -0.098546 5.874281
17 1 0 1.842322 0.123175 -0.827669
18 1 0 3.060426 0.032358 3.652817
19 1 0 -1.766464 -0.056619 3.543046
------
Leucopterin IN BENZENE (anion)
# Opt Freq bpw91/6-311+G(d) pop=nbo geom=check guess=read scrf=(solvent=benzene)
Optimized Parameters
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 0.012823 -0.058653 -0.016293
2 6 0 0.008888 -0.083977 2.272326
3 6 0 1.407973 -0.031259 2.353126
4 6 0 2.180741 0.020578 1.164351
5 8 0 3.433120 0.065805 1.054492
6 6 0 -0.151953 -0.008725 4.773171
7 6 0 1.294041 0.044448 4.855997
8 8 0 1.964304 0.162156 5.915528
9 7 0 2.002683 -0.074495 3.617697
10 7 0 -0.693493 -0.120010 3.437085
11 7 0 -0.698181 -0.081677 1.090475
12 7 0 1.375899 0.001134 -0.025517
13 7 0 -0.630185 -0.154089 -1.249958
14 1 0 -1.635614 -0.006866 -1.158862
15 1 0 -0.231950 0.416919 -1.996550
16 8 0 -0.976758 0.034142 5.735128
17 1 0 1.900449 -0.077277 -0.899470
18 1 0 3.010397 0.075334 3.674716
19 1 0 -1.714360 -0.140809 3.385017
------
Biopterin
First rotamer
# opt freq bpw91/lanl2dz pop=nbo
Input orientation:
------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------
1 6 0 -0.001334 0.027415 0.030556
2 6 0 0.002519 0.288951 2.340249
3 6 0 1.385749 -0.108932 2.444651
4 6 0 2.144086 -0.461890 1.219850
5 8 0 3.346340 -0.820940 1.136064
6 6 0 -0.040243 0.584224 4.656420
7 6 0 1.325083 0.165896 4.761908
8 7 0 2.025592 -0.165769 3.648810
9 7 0 -0.702719 0.645946 3.477947
10 7 0 -0.680550 0.348688 1.133530
11 7 0 1.342749 -0.358935 0.036672
12 7 0 -0.648793 0.076269 -1.182133
13 1 0 -1.623962 0.364066 -1.166460
14 1 0 -0.204865 -0.151924 -2.065769
15 1 0 -0.596477 0.884212 5.548181
16 6 0 2.098125 0.072034 6.071835
17 6 0 1.665645 -1.164307 6.941018
18 6 0 2.341524 -1.125324 8.314023
19 8 0 0.202998 -1.158919 7.184448
20 8 0 3.527400 -0.032009 5.798660
21 1 0 1.922020 0.986376 6.668801
22 1 0 -0.262869 -1.606410 6.435554
23 1 0 1.967136 -2.076062 6.386503