The Problem is ill Posed
If both person 1 states they see person 2 and person 2 states they see person 1 then they must have been in the library at the same time. This is true because at least one of person one and person 3 must be telling the truth as there is only one liar.
To move further we need to further define what it means to lie:
If lying by omission is not lying
In this case people are allowed to have seen people they do not mention without being considered liars. The only way to be considered a liar is to say you saw someone you in fact did not.
If this is the case then:
Any of them could be a liar.
First lets tabulate the statements, if the column header stated they saw the row header then I'll mark that intersection. If it was a corroborated sighting it is marked with an X, if it was a one directional sighting it is marked with a ?
a b c d e i
a \ X ?
b X \ ?
c \ ? X
d ? \
e ? \ ?
i ? X ? \
From this we can see each person stated at least one uncorroborated sighting.
This means that any of them could be the liar: Everyone except the person the liar supposedly saw arrives. Then the liar leaves and the last person arrives. Now everyone would have seen everyone with the exception of the liar and the person they supposedly saw. Since the person they supposedly saw did not claim to see the liar, they did not lie. Thus everyone except the liar only told lies of omission and any of them could have done it.
If the whole truth and nothing but the truth is required
In this case we can make some more deductions.
If neither person 1 states they see person 2 nor person 2 states they see person 1 then either they must not have been in the library at the same time or one of them is the liar. This is true because if they were in the library at the same time at least one of them would have seen the other so then one of them must have omitted seeing the other and is thus lying.
The liar could have been there the entire time. The liar could just be lying by omission. As long as everyone else's testimonies are consistent this should be valid. This means that any consistent system of testimonies with 5 people could be valid with the 6th person being the liar that was there the whole time. Thus we can just examine each 5 person subsystem. Thus the analysis that follows excludes the liar from the the analysis, and anywhere is says people or person, this means truth telling people/person as the liar is excluded from the analysis.
First lets try the full system assuming no liar:
Assuming no lies then here is a table where an X indicates that the row header and column header were in the library at the same time, and a blank indicates they were never in the library at the same time (top half used only for clarity):
a b c d e i
a \ X X X
b \ X X
c \ X X X
d \ X
e \ X
i \
Now if pair 1&2, pair 2&3, and pair 1&3, each have an X then 1,2, and 3 must have all been in the library at the same time. We know this must be true because none of them can reenter the library. WLOG 1 arrived first. 1 must not leave until both 2 and 3 have arrived. WLOG 2 arrives next. 2 must not leave until 3 has arrived. Thus when 3 arrives they will all be there.
There are no sets of 4 people where each pair of people has an X. Thus there was not a time when there were 4 people simultaneously in the library. This means that the periods where there were at least 3 people in the library were never interrupted by a forth person coming or going and can be considered one time unit. (Remember the caveat that the liar is excluded, so the liar my be present simultaneously with three truth tellers)
In the 6 person system there are 4 triplets:
ABE, BEI, CDI, and CEI
If these three triplets exist on the timeline then all of the X's involved with them will be satisfied. The remaining X's that need to be satisfied are:
a b c d e i
a \ X
b \
c \
d \
e \
i \
AD. For each of these pairs (just one in this case) there must be a time period during which only the pair is in the library as none of these pairs is part of a triplet.
Thus a list of occupancies that must have existed at some point during the day are as follows: ABE, BEI, CDI, CEI, and AD
This can be visualized in tabular where the rows are people, the columns are time periods and an O indicates occupancy.
1 2 3 4 5
a O O
b O O
c O O
d O O
e O O O
i O O O
To be a solution the time periods would need to rearrange so that each person occupied the library only during consecutive periods. As expected these periods cannot be arranged in such a manner. Proof for those interested otherwise skip to the next section:
For i's visit to be consecutive periods 2, 3, and 4 must be next to each other. withing that span 2&4 and 3&4 must be consecutive for e and c respectively. That only allows the order 2, 4, 3 or its reverse:
1 2 4 3 5
a O O
b O O
c O O
d O O
e O O O
i O O O
For d to be consecutive 5 must be consecutive with 3, and for e and b to be consecutive 1 must go next to 2, but for a to be consecutive 1 must go next to 5 which is impossible. Thus indeed someone must be lying.
The Possibilities
A lied
Following the same logic as the previous example we can construct tables without A (s A could have been there the whole time if they're lying, This really boils down to removing A from the final period table:
2 4 3
b O
c O O
d O
e O O
i O O O
This is a legitimate possibility. A could be the culprit. Here's a diagram of the library occupancy including who saw who when. Note that A did not see B despite saying they did, whereas everyone else saw only who they said they saw, and no two people were in the library at the same time without one of them seeing the other.
B lied
1 4 3 5
a O O
c O O
d O O
e O O
i O O
Again not possible
C lied
1 2 3 5
a O O
b O O
d O O
e O O
i O O
Again not possible
D lied
1 2 4
a O
b O O
c O
e O O O
i O O
This scenario is also possible so D could be the culprit: Note: that here D said they saw A but they instead saw E. This Solution allows for everyone to see exactly 2 people, which is slightly more in line with the problem statement, so if the problem statement was modified to state that each person saw exactly two people then D would have to be the culprit as if A was the liar they would see a minimum of three people.
E lied
1 2 3 5
a O O
b O O
c O
d O O
i O O
Again not possible
I lied
1 4 3 5
a O O
b O
c O O
d O O
e O O
Again not possible
Conclusion
This problem has two solutions as stated, but could be easily modified to eliminate A as the culprit by stating that each person saw exactly two other people in the library. In that case D is the culprit. Another modification/interpretation that some people took and would result in the same conclusion: The lair included no truth in their statement while the honest students stated the whole truth and nothing but the truth (but this makes the puzzle much easier, and relies on using two different definitions of lying). Yet another modification would be to state that no one, including the liar, saw anyone that they didn't claim to see.