In [18]: a
Out[18]: 
   x1  x2
0   0   5
1   1   6
2   2   7
3   3   8
4   4   9

In [19]: a.x2 = a.x2.shift(1)

In [20]: a
Out[20]: 
   x1  x2
0   0 NaN
1   1   5
2   2   6
3   3   7
4   4   8