A1.

Averages and root-mean-square deviations (rmsd) of corrected values [eq. (20) and Table2], for charging of the guest molecules MAM and ACE in hydrated host molecules CAPO, CHB, CPOS, and CNEG (section “MD simulations”). The correction term was evaluated using eq. (14) for the LS scheme and either eq. (29) or (15) for the BM scheme. The volume V_vdW of the host cavity was approximated by a sphere of radius R_vdW [eq. (29)]. For a given approach and choice of R_vdW, averages over the individual rmsd values are provided.

Guest	Host	Equations (14) and (29), RvdW = 0.5 nm		Equations (14) and (29), RvdW = 0.6 nm		Equations (14) and (29), RvdW = 0.7 nm		Equations (14) and (15)
		(kJ mol−1)	rmsd (kJ mol−1)	(kJ mol−1)	rmsd (kJ mol−1)	(kJ mol−1)	rmsd (kJ mol−1)	(kJ mol−1)	rmsd (kJ mol−1)
MAM	CAPO	−152.1	1.3	−151.5	0.4	−150.6	0.9	−150.6	0.8
	CHB	−187.0	1.4	−186.4	0.7	−185.5	1.1	−185.6	1.0
	CPOS	−18.1	2.5	−17.5	1.9	−16.6	1.5	−16.7	1.5
	CNEG	−395.3	1.8	−394.7	1.6	−393.8	2.1	−393.8	2.1
ACE	CAPO	−68.7	2.7	−69.3	1.8	−70.2	0.6	−70.3	0.5
	CHB	−111.9	2.7	−112.5	1.8	−113.4	0.6	−113.4	0.6
	CPOS	−296.5	3.3	−297.1	2.5	−298.0	1.6	−298.0	1.6
	CNEG	56.1	2.9	55.5	2.5	54.6	2.5	54.6	2.5
(kJ mol−1)			2.3		1.7		1.4		1.3