Assessment of Dispersion-Improved Exchange-Correlation Functionals for the Simulation of CO

Assessment of Dispersion-Improved Exchange-Correlation Functionals for the Simulation of CO2

Binding by Alcoholamines

Hsueh-Chien Li,¹ Jeng-Da Chai,^2,* and Ming-Kang Tsai^1,*

1Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan

2Department of Physics, Center for Theoretical Sciences, and Center for Quantum Science and Engineering, National Taiwan University, Taipei 10617, Taiwan

Supplementary Material

To whom correspondence should be addressed. E-mail: jdchai@phys.ntu.edu.tw and mktsai@ntnu.edu.tw

Figure S1. Local minimum structure of DEA dimer at M06-2X levels.

Min1 TS1 Min2

TS2 Min3

Figure S2. Schematic presentation of trimolecular reaction pathway.

Table S1. Binding energy (in kcal/mol) of complexes a-l using MP2/ATZ optimized geometries.

a b c d e f

ωB97 -5.69 -7.34 -8.60 -5.38 -8.61 -5.26

ωB97X -5.63 -7.32 -8.44 -5.21 -8.49 -5.07

ωB97XD -4.98 -6.85 -8.10 -5.08 -8.74 -5.29

LC-ωPBE -4.39 -6.08 -6.69 -3.37 -6.71 -3.01

CAM-B3LYP -5.23 -6.79 -7.54 -3.93 -7.34 -3.50

B3LYP-GD2 -5.32 -7.13 -8.92 -5.41 -9.28 -5.59

B3LYP-GD3 -5.25 -7.01 -8.51 -5.01 -8.95 -5.16

BLYP-D -4.93 -6.81 -8.54 -5.12 -8.93 -5.27

B97-D -4.31 -6.32 -7.81 -4.73 -8.47 -4.96

M06-2X -5.12 -6.59 -7.99 -4.60 -8.12 -4.81

M05-2X -5.19 -6.63 -7.91 -4.50 -8.05 -4.58

M06HF -4.76 -6.45 -8.06 -4.10 -8.41 -4.62

M06-L -4.58 -6.23 -7.37 -4.31 -7.44 -4.44

B2PLYP -4.34 -5.64 -5.87 -2.76 -5.57 -2.14

B2PLYPD -4.76 -6.17 -7.17 -3.97 -7.19 -3.78

g h i j k l

ωB97 -4.81 -5.63 -11.96 -3.76 -4.85 -4.51

ωB97X -4.56 -5.28 -10.92 -3.57 -4.45 -3.97

ωB97XD -4.88 -6.32 -13.93 -2.86 -3.89 -3.88

LC-ωPBE -2.23 -2.45 -5.88 -2.11 -2.33 -1.33

CAM-B3LYP -2.81 -2.93 -6.67 -2.64 -3.02 -1.94

B3LYP-GD2 -5.24 -6.57 -14.99 -3.16 -4.50 -4.70

B3LYP-GD3 -4.69 -5.94 -13.45 -3.17 -4.47 -4.61

BLYP-D -5.01 -6.27 -14.47 -2.73 -3.97 -4.21

B97-D -4.64 -6.00 -13.46 -2.39 -3.36 -3.63

M06-2X -4.20 -5.27 -12.04 -3.47 -4.74 -4.86

M05-2X -3.88 -4.80 -10.47 -3.35 -4.44 -4.33

M06HF -3.62 -4.80 -10.90 -3.35 -4.58 -4.73

M06-L -4.09 -5.21 -12.33 -2.48 -3.53 -3.89

B2PLYP -1.43 -1.20 -2.50 -2.05 -1.97 -0.47

B2PLYPD -3.23 -3.84 -8.41 -2.70 -3.36 -2.70

Table S2. Binding energy (in kcal/mol) of complexes a-l using the corresponding DFT optimized geometries.

Used NWChem optimized geometries.

a b c d e f

ωB97 -5.71 -7.34 -8.58 -5.37 -8.55 -5.29

ωB97X -5.64 -7.30 -8.37 -5.15 -8.38 -5.09

ωB97XD -4.98 -6.84 -8.06 -5.09 -8.62 -5.36

LC-ωPBE -4.40 -6.09 -6.67 -3.35 -6.65 -3.20

CAM-B3LYP -5.27 -6.83 -7.54 -3.89 -7.36 -3.70

B3LYP-GD2 -5.41 -7.25 -9.05 -5.43¹ -9.46 -5.68

B3LYP-GD3 -5.29 -7.08 -8.58 -5.05 -9.00 -5.29

BLYP-D -5.14 -7.12 -8.99 -3.72 -9.46 -5.58

B97-D -4.46 -6.49 -8.07 -4.63 -8.73 -5.12

M06-2X -5.13 -6.58 -7.98 -4.57 -8.09 -4.90

M05-2X -5.19 -6.61 -7.86 -4.53 -7.97 -4.58

M06HF -4.78 -6.47 -8.26 -4.26 -8.78 -4.76

M06-L -4.58 -6.20 -7.34 -4.34 -7.35 -4.60

B2PLYP -4.35 -5.66 -6.00 -2.87 -5.72 -2.61

B2PLYPD -4.75 -6.18 -7.18 NA -7.18 -3.83

g h i j k l

ωB97 -4.87 -5.71 -12.28 -3.84 -4.33 -4.51

ωB97X -4.55 -5.29 -11.30 -3.61 -4.47 -4.00

ωB97XD -4.86 -6.46 -14.13 -2.89 -3.51 -4.06

LC-ωPBE -2.59 -3.04 -6.80 -2.12 -2.48 -1.64

CAM-B3LYP -3.09 -3.49 -7.86 -2.66 -3.12 -2.18

B3LYP-GD2 -5.36 -6.79 -15.62 -3.20 -4.56 -4.82

B3LYP-GD3 -4.74 -6.08 -13.99 -3.21 -4.55 -4.71

BLYP-D -5.19 -6.51 -15.75 -2.79 -4.11 -4.44

B97-D -4.77 -6.11 -14.36 -2.47 -3.53 -3.91

M06-2X -4.26 -11.03 -21.12 -3.57 -4.22 -4.89

M05-2X -3.90 -4.83 -10.54 -3.40 -4.57 -4.40

M06HF -3.62 -4.85 -11.04 -3.60 -4.39 -5.25

M06-L -4.11 -5.27 -12.71 -2.48 -3.57 -3.89

B2PLYP -2.10 -2.33 -4.43 -2.09 -2.33 -1.11

B2PLYPD -3.21 -3.80 -8.49 -2.72 -3.37 -2.77

Optimized Cartesian coordinate (in Å) of all complexes of C1 Database at MP2/ATZ

a. (H2O)2

O -1.51139800 -0.00295600 -0.12206000 H -0.55881500 -0.00033800 0.05332900 H -1.91607100 0.01852700 0.74870900 O 1.38638600 0.00220900 0.11201500 H 1.73992800 -0.76695200 -0.34564000 H 1.73505900 0.75473500 -0.37603700

b. NH3(H2O)

N -1.37577400 0.02221200 0.00002300 H -1.70581100 -0.28116100 0.90799100 H -1.63464800 -0.69850600 -0.66274500 H -1.90371100 0.85058500 -0.24481300 O 1.54474400 -0.10600700 -0.00011400 H 0.58228200 0.04997800 -0.00033800 H 1.93435300 0.77167200 0.00066200

c. MEA(H2O)

N 0.83508500 1.32273500 0.18645200 H 1.18009000 2.12662500 -0.32449000 H 0.72788100 1.62301300 1.14928000 C -0.46579500 0.90246900 -0.35453900 C -0.91052100 -0.36744500 0.33976100 H -0.34532900 0.70029200 -1.41787900 H -1.24962100 1.65641200 -0.24171700 H -0.20924000 -1.17350100 0.12069900 H -0.92368900 -0.20584600 1.42383100 O -2.22034700 -0.66032900 -0.14107300 H -2.44646500 -1.55389900 0.13333900 O 2.28339300 -1.13700500 -0.09552400 H 1.93981100 -0.22721200 0.01909200 H 3.23449300 -1.03650100 -0.18587600

d. MEA(NH3)

N -0.06462000 1.30115300 -0.55658200 H -0.06364900 2.30868900 -0.66114600 H 0.33024300 0.91933600 -1.40964600 H -1.95022100 0.17897600 -0.20349700 H -3.08829500 -0.86199500 -0.74579300 N -2.61016900 -0.54151900 0.08742700

H -3.31193600 -0.09285400 0.66338600 C 0.79888700 0.90360300 0.55942300 C 0.87644700 -0.60325600 0.61638900 H 0.36210000 1.26585300 1.49107300 H 1.81599100 1.30354900 0.48364900 H 1.48142900 -0.90916000 1.47405700 H -0.12816500 -1.01836600 0.70928400 O 1.49018200 -1.03084600 -0.60612500 H 1.30256500 -1.96678100 -0.72314900

e. DEA(H2O)

C -2.43300000 -0.06993600 0.35237300 C -1.21506200 -0.73233600 -0.25510400 H -2.41183100 -0.18920000 1.44147800 H -2.42069500 0.99794300 0.12500200 H -1.27452000 -1.81617600 -0.09849100 H -1.21163300 -0.55629400 -1.33180100 C 1.21487800 -0.73241600 -0.25512200 C 2.43287300 -0.07012100 0.35236200 H 1.27425300 -1.81626400 -0.09852500 H 1.21145600 -0.55635400 -1.33181500 H 2.42068200 0.99774900 0.12495500 H 2.41166200 -0.18934900 1.44147100 N -0.00007100 -0.14668200 0.30873000 H -0.00006900 -0.30522100 1.31280400 O -3.57405200 -0.71497300 -0.20490700 H -4.36023400 -0.24921900 0.09584800 O 3.57387800 -0.71530100 -0.20485600 H 4.36008700 -0.24945000 0.09568000 O 0.00056500 2.68498300 -0.09757800 H -0.00014400 2.84186100 -1.04563700 H 0.00022100 1.70792900 -0.00040500

f. DEA(NH3)

N -0.09342300 -0.04690700 0.15165500 H -0.19134800 -0.81765300 -0.50319700 H 0.50706400 1.91709700 -0.44816300 N 1.02607400 2.79438800 -0.51126700 H 0.94426600 3.12335800 -1.46558000 C -1.31398800 0.04511100 0.93798700 C -2.50835000 0.19560900 0.02829300

H -1.24953000 0.92232100 1.58758600 H -1.46503600 -0.83368300 1.58155300 H -3.41429400 0.33601200 0.62430400 H -2.36519300 1.06566300 -0.61762700 O -2.59248400 -1.00114900 -0.74729200 H -3.25442900 -0.87490900 -1.43374200 C 1.07722500 -0.30075500 0.98151800 C 2.29246600 -0.51282300 0.11296800 H 0.94169100 -1.17682600 1.63193000 H 1.25115600 0.56889100 1.62007800 H 3.17501100 -0.65209300 0.74303900 H 2.44017800 0.36297300 -0.52134900 O 2.04280700 -1.68329700 -0.67218100 H 2.71537700 -1.73633400 -1.35766300 H 0.54982900 3.47553200 0.06731600

g. (MEA)2

N -1.77075600 1.72820200 0.27185800 H -2.04681700 2.62051800 -0.11996300 H -1.89971500 1.80908300 1.27441900 C -2.62465100 0.65833200 -0.25752600 C -2.09411500 -0.67982100 0.21130800 H -2.58214700 0.69051800 -1.34570600 H -3.67517500 0.74022400 0.03779000 H -1.10259500 -0.84576400 -0.21338400 H -2.01266500 -0.67554400 1.30508300 O -3.02581400 -1.67181400 -0.21709000 H -2.60777300 -2.53312600 -0.12759200 N 1.03729200 0.48201200 -0.63639200 H 0.24558600 1.09279200 -0.44622600 H 1.69597600 0.99421700 -1.21186000 C 1.69266200 0.12701400 0.61769700 C 2.89458600 -0.74184400 0.34000200 H 0.99080700 -0.44068600 1.23293000 H 2.02426000 0.99094700 1.20715800 H 3.33361500 -1.08980200 1.27941100 H 2.58530200 -1.60320400 -0.25726900 O 3.83213100 0.06057700 -0.38384400 H 4.52415900 -0.51385500 -0.72446700

h. MEA(DEA)

N -1.34367400 0.06624700 0.11023100

H -2.14721500 0.15532000 -0.50486000 H 0.59212100 -0.38729500 -0.61299700 N 1.56550900 -0.69090700 -0.57283600 H 1.99618600 -0.46331200 -1.46217800 C -1.24520000 1.26797900 0.92447800 C -1.10256400 2.48191800 0.04003700 H -0.35926300 1.18848900 1.55993200 H -2.11567300 1.40328000 1.58269800 H -0.95566700 3.37495600 0.65387900 H -0.23764200 2.35082800 -0.61569600 O -2.30603900 2.58372500 -0.72290800 H -2.17931200 3.24921700 -1.40586000 C 2.26341200 0.04140100 0.47776400 C 3.72841800 -0.32039300 0.47330800 H 1.84353900 -0.24248900 1.44575100 H 2.18369300 1.13370100 0.38975100 H 4.23636900 0.14977500 1.32012000 H 3.82944900 -1.40594300 0.54623800 O 4.27197900 0.15371600 -0.76250600 H 5.15051400 -0.22214600 -0.87145000 C -1.50765700 -1.13623900 0.91465800 C -1.69304700 -2.33564100 0.01825100 H -2.36072500 -1.06522100 1.60483800 H -0.60399000 -1.28303500 1.51230000 H -1.75586400 -3.24360100 0.62418900 H -0.83948000 -2.41476700 -0.65814100 O -2.90813600 -2.12775600 -0.70771700 H -2.95249000 -2.77675800 -1.41621400

i. (DEA)2

C -0.91182400 2.02579800 0.95484100 C 0.08247000 2.22682600 -0.16965800 H -1.30478600 1.00492500 0.91428100 H -0.40798400 2.15772000 1.91559700 H -0.46361400 2.29313900 -1.12136600 H 0.60015500 3.17796800 -0.02874400 C 2.14784000 1.35470700 -1.09091100 C 3.10305600 0.18629800 -1.07272300 H 1.79003200 1.50650600 -2.11969800 H 2.69453600 2.25391900 -0.79577200 H 3.97562400 0.42041900 -1.68834800 H 3.42371200 -0.00766800 -0.04632600

N 1.05593200 1.14368500 -0.15157100 H 0.57387600 0.26770400 -0.38429300 O -1.95494200 2.98119300 0.77362500 H -2.55586100 2.91601100 1.52228900 O 2.41236500 -0.95359500 -1.60225500 H 3.01350100 -1.70415100 -1.55555200 H 0.04474300 -1.87545500 -1.04751000 N -0.30691600 -1.52396000 -0.16346000 C 0.31307000 -2.27166700 0.93598800 C 0.49104100 -1.41706100 2.18275300 H 1.30301600 -2.59964200 0.61747500 H -0.27755200 -3.16491100 1.18656600 H -0.44408400 -0.88566000 2.40030500 H 0.69739800 -2.07062900 3.03170700 C -1.76202100 -1.59423000 -0.14517900 C -2.33540800 -0.73315300 -1.25006300 H -2.12129200 -1.22004000 0.81559900 H -2.14217300 -2.61918800 -0.25250600 H -2.03921700 0.30830700 -1.09958200 H -1.94009000 -1.06517500 -2.21673000 O -3.75145300 -0.87893100 -1.20251200 H -4.13927800 -0.25785600 -1.82672000 O 1.58256900 -0.52170700 2.09564400 H 1.39857200 0.14489000 1.39824000

j. NH3(CO2)

N -1.99585400 -0.01672300 0.00001200 H -2.33773100 0.93627400 -0.01514100 H -2.39643600 -0.45782700 0.81877300 C 0.94105400 0.00512400 0.00000600 O 0.94355400 1.17539700 0.00000600 O 0.98841300 -1.16391500 0.00000700 H -2.39691400 -0.48397900 -0.80385400

k. MEA(CO2)

N 0.22347900 1.20788300 -0.27534900 H -0.08640500 2.15689300 -0.10263000 H 0.71878200 1.22303300 -1.16050300 C 1.15396100 0.77602800 0.76852100 C 1.73476300 -0.56463500 0.39219000 H 0.60669900 0.66527800 1.70548600 H 1.98073400 1.47525700 0.93513900

H 2.38162300 -0.92752900 1.19502400 H 0.92495900 -1.27918600 0.23184700 O 2.48422300 -0.36793600 -0.81090000 H 2.73629400 -1.22936900 -1.15653500 C -2.14257000 -0.37130600 -0.00589300 O -2.69509300 0.14005500 -0.90065000 O -1.64327700 -0.91895600 0.90177600

l. DEA(CO2)

C 2.42992700 -0.48845800 -0.43643100 C 1.20897400 -1.06560100 0.24603300 H 2.41216300 -0.74163700 -1.50237100 H 2.42055300 0.60083900 -0.34621500 H 1.28734900 -2.16049800 0.25352000 H 1.18825700 -0.73035300 1.28400000 C -1.20939100 -1.06535600 0.24586000 C -2.43012000 -0.48781400 -0.43666600 H -1.28805500 -2.16023300 0.25321900 H -1.18869000 -0.73021700 1.28385900 H -2.42052000 0.60146100 -0.34621300 H -2.41225600 -0.74078200 -1.50265500 N -0.00011300 -0.58227700 -0.41147600 H -0.00007600 -0.90548400 -1.37470000 O 3.57236500 -1.05156500 0.20003200 H 4.35972200 -0.65502700 -0.18502800 O -3.57277700 -1.05079700 0.19951500 H -4.35999000 -0.65395100 -0.18552200 C 0.00031300 2.15680500 0.23863100 O -0.00077300 1.80615300 1.35631400 O 0.00141200 2.56792700 -0.85729000

Table S3. Summary of ∆E!"#(!"→!")!!"#(!) and ∆E!"#(!"→!")!!"#(!) calculations where the values of ∆E are in kcal/mol.

E[CCSD(T)] ∆E[CCSD(T)] E[HF] ∆E[HF] E2 ∆E2 ∆𝐄𝐂𝐁𝐒(!"→!")𝐂𝐂𝐒𝐃(𝐓) ∆E!"#(!"→!")!!"#(!)

a (H2O)2

(aVQZ)

-152.73528 -4.960 -152.13679 -3.640 -0.59848 -1.320 -5.06

-76.36377 -76.06563 -0.29814

-76.36360 -76.06537 -0.29824

(aVTZ)

-152.69296 -4.778 -152.12609 -3.602 -0.56687 -1.176 -4.95

-76.34276 -76.06031 -0.28246

-76.34259 -76.06005 -0.28254

(aVDZ)

-152.55616 -4.374 -152.08813 -3.616 -0.46803 -0.758

-76.27490 -76.04141 -0.23349

-76.27429 -76.04096 -0.23333

b NH3(H2O) (aVQZ)

-132.86967 -6.468 -132.29610 -4.481 -0.57357 -1.987 -6.60

-76.36348 -76.06499 -0.29849

-56.49589 -56.22397 -0.27192

(aVTZ)

-132.83341 -6.283 -132.28717 -4.472 -0.54624 -1.811 -6.52

-76.34251 -76.05969 -0.28282

-56.48088 -56.22035 -0.26053

(aVDZ)

-132.70998 -5.669 -132.25366 -4.429 -0.45632 -1.240

-76.27434 -76.04066 -0.23369

-56.42660 -56.20594 -0.22066

c MEA(H2O) (aVQZ)

-286.51050 -7.761 -285.27521 -4.297 -1.23530 -3.464 -7.93

-210.13471 -209.20366 -0.93104

-76.36343 -76.06469 -0.29873

(aVTZ)

-286.43504 -7.514 -285.25691 -4.283 -1.17813 -3.231 -7.85

-76.34263 -76.05944 -0.28319

-210.08044 -209.19065 -0.88979

(aVDZ)

-286.17555 -6.733 -285.18824 -4.300 -0.98731 -2.433

-76.27496 -76.04075 -0.23421

-209.88986 -209.14064 -0.74922

d MEA(NH3) (aVQZ)

-266.64030 -4.695 -265.43129 -1.709 -1.20901 -2.987 -4.80

-56.49581 -56.22375 -0.27206

-210.13701 -209.20481 -0.93219

(aVTZ)

-266.57082 -4.534 -265.41465 -1.691 -1.15617 -2.843 -4.77

-56.48091 -56.22015 -0.26077

-210.08268 -209.19181 -0.89088

(aVDZ)

-266.32470 -3.999 -265.35015 -1.712 -0.97455 -2.287

-56.42639 -56.20563 -0.22076

-209.89194 -209.14179 -0.75015

e DEA(H2O) (aVTZ)

-440.04111 -7.707 -438.22924 -3.932 -1.81187 -3.775 -8.07

-76.34278 -76.05929 -0.28349

-363.68605 -362.16368 -1.52236

(aVDZ)

-439.64576 -6.892 -438.12497 -3.969 -1.52079 -2.923

-76.27541 -76.04065 -0.23476

-363.35936 -362.07799 -1.28137

f DEA(NH3) (aVTZ)

-420.17938 -4.654 -418.38815 -1.004 -1.79123 -3.650 -4.91

-363.69098 -362.16645 -1.52453

-56.48098 -56.22010 -0.26088

(aVDZ)

-419.79773 -4.078 -418.28821 -1.029 -1.50953 -3.049

-363.36453 -362.08086 -1.28368

-56.42670 -56.20571 -0.22099

g (MEA)2

(aVTZ)

-420.17022 -4.265 -418.38312 -0.227 -1.78710 -4.037 -4.50

-210.08060 -209.19066 -0.88994

-210.08282 -209.19210 -0.89072

(aVDZ)

-419.78838 -3.727 -418.28327 -0.249 -1.50511 -3.478

-209.89022 -209.14075 -0.74947

-209.89222 -209.14212 -0.75010

j NH3(CO2) (aVQZ)

-244.89007 -3.071 -243.94617 -1.836 -0.94389 -1.235 -3.15

-56.49579 -56.22394 -0.27185

-188.38938 -187.71931 -0.67007

(aVTZ)

-244.82603 -2.940 -243.92997 -1.817 -0.89606 -1.123 -3.08

-56.48070 -56.22031 -0.26039

-188.34064 -187.70676 -0.63388

(aVDZ)

-244.61657 -2.608 -243.86938 -1.818 -0.74719 -0.790

-56.42606 -56.20573 -0.22033

-188.18635 -187.66075 -0.52560

k MEA(CO2) (aVQZ)

-398.53313 -4.204 -396.92645 -1.472 -1.60668 -2.732 -4.32

-210.13701 -209.20504 -0.93197

-188.38942 -187.71906 -0.67036

(aVTZ)

-398.42998 -4.022 -396.90096 -1.450 -1.52903 -2.572 -4.24

-210.08258 -209.19202 -0.89056

-188.34099 -187.70663 -0.63436

(aVDZ)

-398.08434 -3.513 -396.80499 -1.27934 -2.046

-209.89167 -209.14191 -0.74975

-188.18707 -187.66074 -0.52633

l DEA(CO2) (aVTZ)

-552.03373 -549.86991 0.363 -2.16382 -4.341 -4.25

-188.34145 -187.70663 -0.63482

-363.68594 -362.16386 -1.52208

(aVDZ)

-551.55300 -3.342 -549.73869 0.355 -1.81431 -3.697

-188.18840 -187.66110 -0.52731

-363.35927 -362.07816 -1.28111